CN114369179A - Photoinitiator composition, photocuring composition and product containing photoinitiator composition - Google Patents
Photoinitiator composition, photocuring composition and product containing photoinitiator composition Download PDFInfo
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- CN114369179A CN114369179A CN202011098705.3A CN202011098705A CN114369179A CN 114369179 A CN114369179 A CN 114369179A CN 202011098705 A CN202011098705 A CN 202011098705A CN 114369179 A CN114369179 A CN 114369179A
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- Prior art keywords
- alkyl
- radical
- group
- phenyl
- substituted
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- 239000000203 mixture Substances 0.000 title claims abstract description 102
- 238000000016 photochemical curing Methods 0.000 title abstract description 28
- -1 oxime ester compounds Chemical class 0.000 claims abstract description 142
- 150000001875 compounds Chemical class 0.000 claims abstract description 138
- 125000005843 halogen group Chemical group 0.000 claims description 69
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 68
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 229920002120 photoresistant polymer Polymers 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 238000006467 substitution reaction Methods 0.000 claims description 31
- 125000001424 substituent group Chemical group 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 25
- 239000000049 pigment Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000002252 acyl group Chemical group 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 125000003435 aroyl group Chemical group 0.000 claims description 7
- 238000003780 insertion Methods 0.000 claims description 7
- 230000037431 insertion Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 6
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 6
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 125000005253 heteroarylacyl group Chemical group 0.000 claims description 6
- 239000000976 ink Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000006850 spacer group Chemical group 0.000 claims description 6
- 239000011593 sulfur Chemical group 0.000 claims description 6
- 239000001055 blue pigment Substances 0.000 claims description 5
- 239000001056 green pigment Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000001054 red pigment Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004946 alkenylalkyl group Chemical group 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 125000004243 coumarin-3-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C(=O)OC2=C1[H] 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000003384 imaging method Methods 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- UXTFKIJKRJJXNV-UHFFFAOYSA-N 1-$l^{1}-oxidanylethanone Chemical compound CC([O])=O UXTFKIJKRJJXNV-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 20
- 239000003999 initiator Substances 0.000 abstract description 13
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- 150000003254 radicals Chemical class 0.000 description 71
- 230000000052 comparative effect Effects 0.000 description 44
- 238000002360 preparation method Methods 0.000 description 37
- 239000000047 product Substances 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000011161 development Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 238000012790 confirmation Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 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 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- GPZXFICWCMCQPF-UHFFFAOYSA-N 2-methylbenzoyl chloride Chemical compound CC1=CC=CC=C1C(Cl)=O GPZXFICWCMCQPF-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 150000001716 carbazoles Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
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- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 230000010933 acylation Effects 0.000 description 2
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- 125000003545 alkoxy group Chemical group 0.000 description 2
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- 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
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- 238000005303 weighing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical class C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 1
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- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 1
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- KXDRZJRGTOBRCU-UHFFFAOYSA-N CCC1=CC(C(C(C=C2)=CC=C2OCC(C(F)F)(F)F)=O)=CC(C2=C3)=C1NC2=CC=C3C(C(C=C1)=CC=C1OCC(C(F)F)(F)F)=O Chemical compound CCC1=CC(C(C(C=C2)=CC=C2OCC(C(F)F)(F)F)=O)=CC(C2=C3)=C1NC2=CC=C3C(C(C=C1)=CC=C1OCC(C(F)F)(F)F)=O KXDRZJRGTOBRCU-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- KGCWZNRZAPIVRY-UHFFFAOYSA-N FC1=CC=C(C(=O)C2=CC=CC=3C4=CC=CC=C4NC23)C=C1 Chemical compound FC1=CC=C(C(=O)C2=CC=CC=3C4=CC=CC=C4NC23)C=C1 KGCWZNRZAPIVRY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- LPPLJAWUBBGPJX-UHFFFAOYSA-N O=C(C(C=C1)=CC=C1OCC(C(F)F)(F)F)C1=CC=CC2=C1NC1=CC=CC=C21 Chemical compound O=C(C(C=C1)=CC=C1OCC(C(F)F)(F)F)C1=CC=CC2=C1NC1=CC=CC=C21 LPPLJAWUBBGPJX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
- GHXXDRXSFYGBLJ-UHFFFAOYSA-N [9-ethyl-6-(4-fluorobenzoyl)carbazol-3-yl]-(4-fluorophenyl)methanone Chemical compound C(C)N1C2=CC=C(C=C2C=2C=C(C=CC1=2)C(=O)C1=CC=C(C=C1)F)C(=O)C1=CC=C(C=C1)F GHXXDRXSFYGBLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229930014669 anthocyanidin Natural products 0.000 description 1
- 150000001453 anthocyanidins Chemical class 0.000 description 1
- 235000008758 anthocyanidins Nutrition 0.000 description 1
- 229930002877 anthocyanin Natural products 0.000 description 1
- 235000010208 anthocyanin Nutrition 0.000 description 1
- 239000004410 anthocyanin Substances 0.000 description 1
- 150000004636 anthocyanins Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 150000001634 bornane-2,3-dione derivatives Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- GUPWNYUKYICHQX-UHFFFAOYSA-N carbonobromidic acid Chemical compound OC(Br)=O GUPWNYUKYICHQX-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 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
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Indole Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a photoinitiator composition, a photocuring composition and a product containing the same. The photoinitiator composition comprises: acylcarbazole derivatives and oxime ester compounds; wherein the acylcarbazole derivative is one or more selected from the group consisting of a compound represented by formula I, a compound represented by formula II-A, a compound represented by formula II-B, a compound represented by formula II-C, a compound represented by formula II-D, a compound represented by formula II-E, a compound represented by formula II-F, a compound represented by formula II-G, a compound represented by formula II-H and a compound represented by formula II-I; the oxime ester compound is a compound shown as a formula (III). In the photoinitiator, the acylcarbazole derivative with a specific structure and the oxime ester compound are matched for use, and the initiator has excellent sensitivity and thermal stability through the synergistic effect of the acylcarbazole derivative and the oxime ester compound, and simultaneously, the photocuring efficiency and the developing effect of the photoinitiator can be greatly improved.
Description
Technical Field
The invention relates to the technical field of photocuring, in particular to a photoinitiator composition, a photocuring composition and a product containing the same.
Background
Photocuring technology has been widely used since the 70 s, for example, UV photocuring technology is commonly used in the fields of coatings, printing inks, and electronic device manufacturing, wherein the key factors influencing curing efficiency are photoinitiators and co-initiator components used in combination with the photoinitiators, such as sensitizers. Carbazolyl oxime esters are an important class of oxime ester photoinitiators, which are well known and studied and used by those skilled in the art due to their relatively high sensitivity. The need for improved color saturation or hiding power has led to higher and higher pigment levels in photocurable formulations, especially for high pigment black photoresists, but this has led to a reduction in the efficiency of light energy utilization during curing due to pigment absorption, and thus the development of photoinitiators or photoinitiator compositions with higher sensitivity is desired.
Some sensitizers have been reported in the literature, including benzophenones and derivatives thereof, thioxanthones and derivatives thereof, anthraquinones and derivatives thereof, coumarin derivatives, camphorquinones, phenothiazines and derivatives thereof, 3- (aroylmethylene) thiazolines, rhodanines and derivatives thereof, eosins, rhodamines, acridines, anthocyanins, merocyanine dyes, tertiary amine compounds; it is preferably benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, and coumarin derivatives. However, the above-mentioned sensitizer does not exhibit satisfactory sensitizing effect when used in combination with an oxime ester. Some compounds reduce the photocuring efficiency of photocurable composition formulations by containing phenolic hydroxyl or anilino groups (e.g., eosin, anthocyanidin, phenothiazine). In the preferred four classes of compounds, although they are themselves photoinitiators, the photoinitiation efficiency is much lower than that of the oxime ester compounds and they do not exhibit synergistic sensitization when used in combination with oxime esters. At the same time, the sensitizer needs to have good thermal stability and developing effect.
In view of the above problems, it is desirable to provide a sensitizer which has good sensitivity, high photocuring efficiency, good thermal stability and good developing effect.
Disclosure of Invention
The invention mainly aims to provide a photoinitiator composition, a photocuring composition and a product containing the same, and aims to solve the problems that the existing sensitizer cannot simultaneously meet the requirements of good sensitivity, high photocuring efficiency, good thermal stability and good developing effect.
In order to achieve the above object, the present invention provides, in one aspect, a photoinitiator composition comprising: acylcarbazole derivatives and oxime ester compounds; wherein the acylcarbazole derivative is one or more selected from the group consisting of a compound represented by formula I, a compound represented by formula II-A, a compound represented by formula II-B, a compound represented by formula II-C, a compound represented by formula II-D, a compound represented by formula II-E, a compound represented by formula II-F, a compound represented by formula II-G, a compound represented by formula II-H and a compound represented by formula II-I; the oxime ester compound is a compound shown as a formula (III);
wherein R is1，R2，R4，R5，R7，R8，R24，R25，R27，R28，R34，R35，R37，R38，R41，R42，R44，R45，R47，R48，R54，R55，R61，R62，R67，R68，R71，R72，R74，R75，R102-R108，R112，R114，R115，R117，R118，R121，R122，R124-R127Each independently being H, a halogen atom, C1-C8Alkyl radical, C1-C8Alkoxy, CN;
R70is selected from H or C1-C10Alkoxy radical, R73Selected from H, C6-C20Aroyl radical, C6-C20At least one hydrogen atom of the aroyl group being substituted by a halogen atom, and/or in C6-C20A substituent formed by inserting an O atom into the side chain of the aroyl;
R6，R26，R36，R46，R56，R66，R106，R116each independently selected from H, halogen atom, CN, C1-C8Alkyl radical, C1-C12Alkyl acyl radical, C5-C6Substituted C1-C3Alkyl acyl radical, C6-C20Aroyl radical, C4-C20(ii) a heteroaryl acyl group,
or R6，R26，R36，R46，R56，R66，R106，R116Respectively form 5-7 membered rings with adjacent substituents, wherein C6-C20Aroyl and C4-C20Substituents on the heteroaroyl group include halogen atoms, R40、OR50、SR50、NR51R52、COOR50Or CONR51R52；
When R is116Is C6-C20Aroyl or C4-C20In the case of heteroarylacyl, the ortho-substituent of the acyl group on the aromatic or heteroaromatic ring is attached to any carbon atom on the carbazole ring;
R9，R29，R39，R49，R59，R69each independently selected from C1-C12Straight or branched alkyl, C2-C12Alkenyl radical, C3-C12Alkenylalkyl, or C1-C12Straight or branched alkyl, C2-C12Alkenyl radical, C3-C12A first group formed by substitution of a hydrogen in an alkenylalkyl group with one or more of the following substituents: phenyl radical, C5-C6Cycloalkyl radical, C3-C6Heterocyclyl, halogen, COOR20、OR20、SR20、PO(OCnH2n+1)2、Si(CnH2n+1)3N is an integer of 1 to 4; or
R9，R29，R39，R49，R59，R69Each independently selected from C3-C12Alkyl and/or C3-C12Alkenylalkyl with one or more O, S, SO insertions in the carbon chain2CO or COO; or R9，R29，R39，R49，R59，R69Each independently selected from C2-C12Alkylene and/or C4-C12Alkylene containing double bonds, and C2-C12Alkylene or C4-C12Radicals bound to the double bond-containing alkylene end and R9，R29，R39，R49，R59，R69The groups to which each is attached are the same; or
R9，R29，R39，R49，R59，R69Each independently selected from phenyl, or a second group formed by phenyl substituted with one or more of the following substituents: c1-C8Alkyl, halogen atom, OR20、SR20、COR30、CN、COOH；
R10，R110，R120，R130Each independently selected from C1-C12Alkyl or C6-C20An aryl group;
Ar1，Ar2，Ar3，Ar4，Ar5，Ar6，Ar7，Ar8，Ar9each independently selected from C6-C20Aryl radical, C4-C20Heteroaryl, or C6-C20Aryl and C4-C20At least one H on the heteroaromatic group is substituted with a group formed by: halogen atom, CN, R40，OR50，SR50，NR51R52，COOR50，CONR51R52Wherein Ar is1，Ar2，Ar5The ortho position of the acyl group can be connected with any carbon atom on the carbazole ring through O and S atoms, and Ar1Phenyl, o-methylphenyl and p-methylphenyl are excluded;
y is selected from C1-C3A linear or branched alkylene group; m, n are each independently selected from 0 or 1;
in the formula (III), Ar9A third group selected from arylthioaryl, fluoren-2-yl, benzofluorenyl or coumarin-3-yl having the parent structure or a group in which a hydrogen in the third group is substituted by one or more of the following substituents: halogen atom, nitro group, R11A
The substitution is carried out by the following steps,
m1is 0 or 1;
a is selected from a direct bond, O, S, CO or R11' N, and R11' is C1-C12An alkyl group;
R11is selected from C1～C12Alkyl, C interrupted by one or more oxygen or sulfur atoms3～C12Alkyl radical, C3～C8Cycloalkyl of, C3～C8Heterocyclic group, C2～C7Alkenylmethyl, C6～C15Aryl or C4～C15Heteroaryl, and C6～C15Aryl and C4～C15The hydrogen atoms in the heteroaryl groups may be replaced by fluorine atoms, or C1-C4Alkylsulfonyl substituted, and C1～C4The hydrogen atom of the alkyl group may be replaced by F, C1-C4Alkoxy, OH, OOCR14、COOR19、(R19O)2P(O)、(CH3)3Si or phenyl substituted, R19Is C1-C4An alkyl group; or R11Or R11' form a 5-7 membered ring with the atom on the adjacent parent, or R11R11' N is a cyclic substituent; or
Ar9Form a 5-7 membered ring with an adjacent substituent;
R13is C1-C16Alkyl, phenyl, C4-C7Cycloalkyl radical, C1-C16Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO or R40Radicals formed by OOC substitution, C3-C16Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO or R40OOC substituted and interrupted by at least one oxygen or sulfur atom, or phenyl hydrogen atoms interrupted by at least one halogen atom, C1-C12Alkyl radical, C1-C4Alkoxy, CN-substituted radicals, or R13To adjacent Ar9Joined to form a 5-to 7-membered ring, R14Is selected from C1-C11Alkyl radical, C3-C5Alkenyl radical, C1-C4Alkoxy, phenoxy, phenyl, C1-C11Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7A group formed by substituting cycloalkyl or CN, or a group formed by substituting hydrogen atom in phenyl with at least one halogen atom, C1-C4Alkyl radical, C1-C4Alkoxy, CN isA group formed by substitution;
R20and R30Each independently selected from H, C1-C8Alkyl through one or more of F, Cl, OH, C5-C6C formed by substitution of cycloalkyl1-C8Alkyl, containing one or more O or S spacers, and interrupted by hydroxy and/or OOCR4Substituted C3-C8Alkyl, five-or six-membered rings containing one or 2 heteroatoms O, S, N, phenyl, via one or more halogen atoms or C1-C4Alkyl-substituted phenyl;
R40and R50Each independently selected from C1-C8Alkyl radical, C1-C8Radicals formed by substitution of alkyl radicals by at least one F, Cl or hydroxy radical, C3-C8Radicals formed by insertion of one or more oxygen atoms in the alkyl radical and substitution of at least one hydrogen atom by a hydroxyl and/or acetoxy radical, five-or six-membered rings containing 1-2 heteroatoms, phenyl, or C1-C4An alkyl phenyl group;
R51and R52Each independently selected from C1-C4Alkyl, C substituted by hydroxy1-C4Alkyl, or NR51R52Is a cyclic substituent.
Further, the compound represented by the formula I is selected from one or more compounds represented by the formulae (I-1) to (I-36):
further, the compound represented by the formula II-A, the compound represented by the formula II-B, the compound represented by the formula II-C, the compound represented by the formula II-D, the compound represented by the formula II-E, the compound represented by the formula II-F, the compound represented by the formula II-G and the compound represented by the formula II-H are selected from one or more of the following organic substances:
further, the oxime ester compound shown in the formula III is selected from one or more of the following compounds:
wherein, Y1，Y2Each independently is H, C1-C12Alkyl, nitro, Ar10CO or
m2，n1，n2Each independently is 1 or 0;
Ar10is C6-C15Aryl or C4-C15Heteroaryl, in which hydrogen on carbon is optionally replaced by fluorine atom, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfonyl substituted, and C1-C4Hydrogen in the alkyl radical being bound by fluorine atoms, C1-C4Alkoxy or R14COO substitution;
R17，R18each independently is H, C1-C8Alkyl, C interrupted by one or 2 oxygen atoms3-C8Alkyl radical, C2-C7Alkenylmethyl, phenyl; hydrogen of alkyl and phenyl optionally substituted by halogen atoms, C4-C7Cycloalkyl, hydroxy, R14COO、COOR19、(R19O)2P(O)、(CH3)3Si and phenyl substitution; r19Is C1-C4Alkyl, or R17，R18Each independently may form a 5 to 7 membered ring with the adjacent substituents and atoms on the parent;
R15，R16，R21，R22，R71，R72，R73，R74，R75each independently is H, C1-C8Alkyl radical, C1-C8Alkoxy group, halogen atom, CN,
C6-C15Aromatic acyl radical, C4-C15Heteroaromatic acyl group, C1-C8Hydrogen in alkyl by one or more halogen atoms, C4-C7Cycloalkyl, hydroxy, CN, R14COO-substituted substituent, C6-C15Aryl and/or C4-C15A group formed by substituting hydrogen on a heteroaryl group with one or more of the following: H. halogen atom, CN, R40、OR50、SR50、NR51R52、COOR50Or CONR51R52Or adjacent substituents may form a 5 to 7 membered ring;
R13' is C1-C16Alkyl, phenyl, C4-C7Cycloalkyl radical, C1-C16Hydrogen in the alkyl radical being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO for the radical formed, C3-C16Hydrogen in the alkyl radical being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, a group substituted by hydroxy and/or interrupted by at least one oxygen or sulphur atom, the hydrogen of the phenyl group being interrupted by at least one halogen atom, C1-C12Alkyl radical, C1-C4Alkoxy and CN; r13Is' a C1-C16Alkyl radicals, substituted by one or more halogen atoms, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R4COO、R20OOC-substituted C1-C16 alkyl, substituted by one or more halogen atoms, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy-substituted C interrupted by one or more oxygen, sulfur atoms3-C16Alkyl, phenyl, substituted by one or more halogen atoms, C1-C12Alkyl radical, C1-C4Alkoxy, CN-substituted phenyl, C4-C7A cycloalkyl group; or R13' may be linked to an adjacent benzene ring to form a 5-to 7-membered five-to seven-membered ring;
R40，R50each independently selected from H, C1-C8Alkyl radical, C1-C8The hydrogen in the alkyl group being reacted with one or more of F, Cl, OH, C3-C7Radicals formed by cycloalkyl substitution, C3-C8Alkyl interrupted by one or more O and/or S, and hydrogen interrupted by hydroxy and/or OOCR4Radicals formed by substitution of five-or six-membered rings containing one or two heteroatoms O, S, N, phenyl, or C1-C4An alkyl phenyl group;
R51，R52each independently selected from C1-C4Alkyl, C substituted by hydroxy1-C4An alkyl group; or NR51R52Is selected from
Further, the oxime ester compound shown in the formula III is selected from one or more of the following compounds:
further, the molar ratio of the acylcarbazole derivative to the oxime ester compound is (0.1-1.4): 1; preferably, the molar ratio of the acylcarbazole derivative to the oxime ester compound is (0.2-1): 1.
In another aspect, there is provided a photocurable composition comprising a photoinitiator and a free-radically polymerizable compound, the photoinitiator comprising the photoinitiator composition provided herein.
Further, the radical polymerizable compound is one or more selected from the group consisting of an acrylate compound, a methacrylate compound, and an acrylate or methacrylate group-containing resin.
Further, the photoinitiator composition according to any one of claims 1 to 6 is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photocurable composition; preferably, the photoinitiator composition is used in an amount of 1 to 8 parts by weight based on 100 parts by weight of the photocurable composition.
In another aspect of the present application, there is also provided a photocurable product containing the photocurable composition provided herein.
Further, the photo-curable product includes an ink, a coating, an adhesive, or a 3D imaging composition.
Yet another aspect of the present application also provides a photoresist comprising: the photoinitiator composition, the multifunctional acrylate monomer, the alkali-soluble resin and the solvent.
Further, the photoresist also comprises a pigment, and the pigment is selected from one or more of red pigment, green pigment and blue pigment.
Further, the photoresist also comprises pigment, and the pigment is selected from carbon black and/or titanium black.
The application also provides a color matrix which is prepared by the photoresist, and the pigment in the photoresist is selected from one or more of red pigment, green pigment and blue pigment.
In another aspect, the present application further provides a black matrix prepared by using the photoresist, wherein the pigment in the photoresist is selected from carbon black and/or titanium black.
The application also provides a light spacer which is prepared by the photoresist, and the pigment in the photoresist is selected from carbon black and/or titanium black.
The application further provides a color filter device, and the color filter device is prepared by taking the photoresist as a raw material.
By applying the technical scheme of the invention, the acylcarbazole derivative and the oxime ester compound with specific structures are matched and used in the photoinitiator, and the photoinitiator has excellent sensitivity and thermal stability through the synergistic effect of the acylcarbazole derivative and the oxime ester compound, and simultaneously, the photocuring efficiency and the developing effect of the photoinitiator can be greatly improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the conventional sensitizer cannot simultaneously satisfy the problems of good sensitivity, high photocuring efficiency, good thermal stability and good developing effect. In order to solve the above technical problems, the present application provides a photoinitiator composition comprising: acylcarbazole derivatives and oxime ester compounds; wherein the acylcarbazole derivative is one or more selected from the group consisting of a compound represented by formula I, a compound represented by formula II-A, a compound represented by formula II-B, a compound represented by formula II-C, a compound represented by formula II-D, a compound represented by formula II-E, a compound represented by formula II-F, a compound represented by formula II-G, a compound represented by formula II-H and a compound represented by formula II-I; the oxime ester compound is a compound shown as a formula (III);
wherein R is1，R2，R4，R5，R7，R8，R24，R25，R27，R28，R34，R35，R37，R38，R41，R42，R44，R45，R47，R48，R54，R55，R61，R62，R67，R68，R71，R72，R74，R75，R102-R108，R112，R114，R115，R117，R118，R121，R122，R124-R127Each independently being H, a halogen atom, C1-C8Alkyl radical, C1-C8Alkoxy, CN;
R70is selected from H or C1-C10An alkoxy group; r73Selected from H, C6-C20Aroyl radical of said C6-C20At least one hydrogen atom in aroyl group being substituted by a halogen atom, and/or at said C6-C20A substituent formed by inserting an O atom into the side chain of the aroyl;
R6，R26，R36，R46，R56，R66，R106，R116each independently selected from H, halogen atom, CN, C1-C8Alkyl radical, C1-C12Alkyl acyl radical, C5-C6Substituted C1-C3Alkyl acyl radical, C6-C20Aroyl radical, C4-C20(ii) a heteroaryl acyl group,
or R6，R26，R36，R46，R56，R66，R106，R116Respectively form 5-7 membered rings with adjacent substituents, wherein C6-C20Aroyl and C4-C20Substituents on the heteroaroyl group include halogen atoms, R40、OR50、SR50、NR51R52、COOR50Or CONR51R52；
When R is116Is C6-C20Aroyl or C4-C20In the case of heteroarylacyl, the ortho-substituent of the acyl group on the aromatic or heteroaromatic ring is attached to any carbon atom on the carbazole ring;
R9，R29，R39，R49，R59，R69each independently selected from C1-C12Straight or branched alkyl, C2-C12Alkenyl radical, C3-C12Alkenylalkyl, or C1-C12Straight or branched alkyl, C2-C12Alkenyl radical, C3-C12A first group formed by substitution of a hydrogen in an alkenylalkyl group with one or more of the following substituents: phenyl radical, C5-C6Cycloalkyl radical, C3-C6Heterocyclyl, halogen, COOR20、OR20、SR20、PO(OCnH2n+1)2、Si(CnH2n+1)3N is an integer of 1 to 4; or
R9，R29，R39，R49，R59，R69Each independently selected from C3-C12Alkyl and/or C3-C12Alkenylalkyl with one or more O, S, SO insertions in the carbon chain2CO or COO; or R9，R29，R39，R49，R59，R69Each independently selected from C2-C12Alkylene and/or C4-C12Alkylene containing double bonds, and C2-C12Alkylene or C4-C12Radicals bound to the double bond-containing alkylene end and R9，R29，R39，R49，R59，R69The groups to which each is attached are the same; or
R9，R29，R39，R49，R59，R69Each independently selected from phenyl, or a second group formed by phenyl substituted with one or more of the following substituents: c1-C8Alkyl, halogen atom, OR20、SR20、COR30、CN、COOH；
R10，R110，R120，R130Each independently selected from C1-C12Alkyl or C6-C20An aryl group;
Ar1，Ar2，Ar3，Ar4，Ar5，Ar6，Ar7，Ar8，Ar9each independently selected from C6-C20Aroyl radical, C4-C20Heteroaroyl, and C6-C20Aryl and C4-C20And at least one H on the heteroaromatic group is substituted by the following group: halogen atom, CN, R40，OR50，SR50，NR51R52，COOR50，CONR51R52Wherein Ar is1，Ar2，Ar5The ortho position of the acyl group can be connected with any carbon atom on the carbazole ring through O and S atoms, and Ar1Phenyl, o-methylphenyl and p-methylphenyl are excluded;
y is selected from C1-C3A linear or branched alkylene group; m, n are each independently selected from 0 or 1;
in the formula (III), Ar9A third group selected from arylthioaryl, fluoren-2-yl, benzofluorenyl or coumarin-3-yl having the parent structure or a group in which a hydrogen in the third group is substituted by one or more of the following substituents: halogen atom, nitro group, R11A
The substitution is carried out by the following steps,
m1is 0 or 1;
a is selected from a direct bond, O, S, CO or R11' N, and R11' is C1-C12An alkyl group; r11Is selected from C1～C12Alkyl, C interrupted by one or more oxygen or sulfur atoms3～C12Alkyl radical, C3～C8Cycloalkyl of, C3～C8Heterocyclic group, C2～C7Alkenylmethyl, C6～C15Aryl or C4～C15Heteroaryl, and C6～C15Aryl and C4～C15The hydrogen atoms in the heteroaryl groups may be replaced by fluorine atoms, or C1-C4Alkylsulfonyl substituted, and C1～C4The hydrogen atom of the alkyl group may be replaced by F, C1-C4Alkoxy, OH, OOCR14、COOR19、(R19O)2P(O)、(CH3)3Si or phenyl substituted, R19Is C1-C4An alkyl group; or R11Or R11' form a 5-7 membered ring with the atom on the adjacent parent, or R11R11' N is a cyclic substituent (optionally
Or Ar9Form a 5-7 membered ring with an adjacent substituent; r13Is C1-C16Alkyl, phenyl, C4-C7Cycloalkyl radical, C1-C16Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO or R40Radicals formed by OOC substitution, C3-C16Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO or R40OOC substituted and interrupted by at least one oxygen or sulfur atom, or phenyl hydrogen atoms interrupted by at least one halogen atom, C1-C12Alkyl radical, C1-C4Alkoxy, CN-substituted radicals, or R13To adjacent Ar9Joined to form a 5-to 7-membered ring, R14Is selected from C1-C11Alkyl radical, C3-C5Alkenyl radical, C1-C4Alkoxy, phenoxy, phenyl, C1-C11Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7A group formed by substituting cycloalkyl or CN, or a group formed by substituting hydrogen atom in phenyl with at least one halogen atom, C1-C4Alkyl radical, C1-C4Alkoxy and CN; r20And R30Each independently selected from H, C1-C8Alkyl through one or more of F, Cl, OH, C5-C6C formed by substitution of cycloalkyl1-C8Alkyl, containing one or more O or S spacers, and interrupted by hydroxyAnd/or OOCR4Substituted C3-C8Alkyl, five-or six-membered rings containing one or 2 heteroatoms O, S, N, phenyl, via one or more halogen atoms or C1-C4Alkyl-substituted phenyl; r40And R50Each independently selected from C1-C8Alkyl radical, C1-C8Radicals formed by substitution of alkyl radicals by at least one F, Cl or hydroxy radical, C3-C8Groups formed by insertion of one or more oxygen atoms into the alkyl radical and substitution of at least one hydrogen atom by a hydroxyl and/or acetoxy group, five-or six-membered rings containing 1-2 heteroatoms, phenyl, or C1-C4An alkyl phenyl group; r51And R52Each independently selected from C1-C4Alkyl, C substituted by hydroxy1-C4Alkyl, or NR51R52Is a cyclic substituent.
In the photoinitiator, the acylcarbazole derivative with a specific structure and the oxime ester compound are matched for use, and the initiator has excellent sensitivity and thermal stability through the synergistic effect of the acylcarbazole derivative and the oxime ester compound, and simultaneously, the photocuring efficiency and the developing effect of the photoinitiator can be greatly improved.
The acyl carbazole derivative and the oxime ester compound have a plurality of substituents, and the type capable of further improving the synergistic effect of the acyl carbazole derivative and the oxime ester compound can be screened out through the optimization of the substituents. In a preferred embodiment, the compound of formula I is selected from one or more of the compounds of formulae (I-1) to (I-32):
in a preferred embodiment, the compound of formula II-A, II-B, II-C, II-D, II-E, II-F, II-G and II-H are selected from one or more of the following organic compounds:
in a preferred embodiment, the oxime ester compound of formula III is selected from one or more of the following compounds:
wherein, Y1，Y2Each independently is H, C1-C12Alkyl, nitro, Ar10CO or
m2，n1，n2Each independently is 1 or 0;
Ar10is C6-C15Aryl or C4-C15Heteroaryl, in which hydrogen on carbon is optionally replaced by fluorine atom, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfonyl substituted, and C1-C4Hydrogen in the alkyl radical being bound by fluorine atoms, C1-C4Alkoxy or R14COO substitution;
R17，R18each independently is H, C1-C8Alkyl, C interrupted by one or 2 oxygen atoms3-C8Alkyl radical, C2-C7Alkenylmethyl, phenyl; hydrogen of alkyl and phenyl optionally substituted by halogen atoms, C4-C7Cycloalkyl, hydroxy, R14COO、COOR19、(R19O)2P(O)、(CH3)3Si and phenyl substitution; r19Is C1-C4Alkyl, or R17，R18Each independently may form a 5 to 7 membered ring with the adjacent substituents and atoms on the parent;
R15，R16，R21，R22，R71，R72，R73，R74，R75each independently is H, C1-C8Alkyl radical, C1-C8Alkoxy group, halogen atom, CN,
C6-C15Aromatic acyl radical, C4-C15Heteroaromatic acyl group, C1-C8Hydrogen in alkyl by one or more halogen atoms, C4-C7Cycloalkyl, hydroxy, CN, R14COO-substituted substituent, C6-C15Aryl and/or C4-C15A group formed by substituting hydrogen on a heteroaryl group with one or more of the following: H. halogen atom, CN, R40、OR50、SR50、NR51R52、COOR50Or CONR51R52Or adjacent substituents may form a 5 to 7 membered ring;
R13' is C1-C16Alkyl, phenyl, C4-C7Cycloalkyl radical, C1-C16Hydrogen in the alkyl radical being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO for the radical formed, C3-C16Hydrogen in the alkyl radical being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy-substituted and/orA group formed by insertion of at least one oxygen or sulfur atom, a hydrogen in a phenyl group being interrupted by at least one halogen atom, C1-C12Alkyl radical, C1-C4Alkoxy and CN; r13Is' a C1-C16Alkyl radicals, substituted by one or more halogen atoms, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R4COO、R20OOC substituted C1-C16Alkyl radicals, substituted by one or more halogen atoms, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy-substituted C interrupted by one or more oxygen, sulfur atoms3-C16Alkyl, phenyl, substituted by one or more halogen atoms, C1-C12Alkyl radical, C1-C4Alkoxy, CN-substituted phenyl, C4-C7A cycloalkyl group; or R13' may be linked to an adjacent benzene ring to form a 5-to 7-membered five-to seven-membered ring;
R40，R50each independently selected from H, C1-C8Alkyl radical, C1-C8The hydrogen in the alkyl group being reacted with one or more of F, Cl, OH, C3-C7Radicals formed by cycloalkyl substitution, C3-C8Alkyl interrupted by one or more O and/or S, and hydrogen interrupted by hydroxy and/or OOCR4Substituted C3-C8Alkyl-forming radicals, five-or six-membered rings containing one or two heteroatoms O, S, N, phenyl, or C1-C4An alkyl phenyl group;
R51，R52each independently selected from C1-C4Alkyl, C substituted by hydroxy1-C4An alkyl group; or NR51R52Is selected from
The oxime ester compound with the structure is similar to the acyl carbazole derivative required by the application, so that the oxime ester compound has better compatibility, which is beneficial to further improving the synergistic effect of the oxime ester compound and the acyl carbazole derivative, and is further beneficial to improving the sensitivity, the thermal stability and the developing effect of the photoinitiator composition. More preferably, the oxime ester compound of formula iii is selected from one or more of the following compounds:
In order to further improve the comprehensive performances of the photoinitiator composition such as sensitivity, development effect and the like, the photoinitiator composition is preferably prepared by selecting the compounds shown by IV-A and/or IV-B and the acylcarbazole derivatives provided by the application.
The preparation method of the acylcarbazole derivative compounds shown in the formula I, the formulas II-A-II-E and the formulas II-G comprises the following steps: corresponding substituted carbazole or benzocarbazole and corresponding acylation reagent (such as acyl chloride or acid anhydride) are subjected to one or two Friedel-crafts acylation reaction to obtain an acylation product; when a reactive substituent on the aroyl or heteroaroyl group is desired to continue the reaction, the reaction is continued with a corresponding reagent, for example, a fluorine atom is substituted with an alkoxy, alkylthio, secondary amino, phenoxy, phenylthio or the like; esterification of carboxylic acids with an alcohol compound, etc., to give the final compounds of formulae I, formulae II-A to II-E, and formulae II-G.
The preparation method of II-F comprises the following steps: carrying out N substitution reaction on corresponding 1-position and 9-position unsubstituted carbazole compounds and o-bromobenzoic acid to obtain an N- (carboxyl phenyl) carbazole derivative intermediate; the intermediate is catalyzed by concentrated sulfuric acid or polyphosphoric acid and other acids and condensed into ring to obtain IIF.
The preparation method of II-H comprises the following steps: taking corresponding 1-position, 6-position and 9-position unsubstituted carbazole compounds as raw materials, and reacting with bromo-carboxylic acid to carry out N-alkylation; secondly, carrying out condensation reaction by using an acid catalyst or acylating and acylating carboxylic acid to obtain a benzocyclocarbazole derivative; and thirdly, carrying out corresponding Friedel-crafts acylation reaction to obtain II-H.
One of the methods for preparing oxime ester compounds is to esterify the corresponding intermediate oxime compound with an acid chloride or an acid anhydride to obtain an oxime ester.
Preparation of photoinitiator composition: the components are directly mixed, or the components are dissolved in a solvent to form a solution, or the components are dissolved in a light-cured composition formula, wherein the formula comprises necessary components such as resin, monomer and the like.
In a preferred embodiment, the molar ratio of the acylcarbazole derivative to the oxime ester compound is (0.1-1.4): 1; more preferably, the molar ratio of the acylcarbazole derivative to the oxime ester compound is (0.2-1): 1.
In another aspect, there is provided a photocurable composition comprising a photoinitiator and a free-radically polymerizable compound, the photoinitiator comprising the photoinitiator composition provided herein.
In the photoinitiator, the acylcarbazole derivative with a specific structure and the oxime ester compound are matched for use, and the initiator has excellent sensitivity and thermal stability through the synergistic effect of the acylcarbazole derivative and the oxime ester compound, and simultaneously, the photocuring efficiency and the developing effect of the photoinitiator can be greatly improved. The photo-curing composition containing the photoinitiator and the free radical polymerizable compound also has better sensitivity, thermal stability, photo-curing efficiency and developing effect.
The radical polymerizable compound used in the above-mentioned photocurable composition may be selected from those commonly used in the art, such as (meth) acrylate compounds and/or (meth) acrylate group-containing resins.
In a preferred embodiment, the above free radical polymerizable compound is a low molecular weight double bond compound including, but not limited to, one or more of the group consisting of alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, and dialkylaminoalkyl methacrylates. More preferred are methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, silicone acrylate, acrylonitrile, vinyl acetate, vinyl ether, styrene, N-vinylpyrrolidone, and the like.
In a preferred embodiment, the above-mentioned radical polymerizable compound is a compound having two or more double bonds, including, but not limited to, one or more of the group consisting of ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, diacrylate of 1, 6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate.
In a preferred embodiment, the radical polymerizable compound is a higher molecular weight double bond compound, which includes but is not limited to one or more of the group consisting of an acrylated epoxy resin, an acrylated polyester resin, an unsaturated polyester resin, an acrylated polyether resin and an acrylated polyurethane resin, and the molecular weight is generally 500 to 3000.
In order to further improve the overall performance of the photocurable composition, in a preferred embodiment, the photoinitiator composition is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photocurable composition. More preferably, the photoinitiator composition provided by the present application is used in an amount of 1 to 8 parts by weight based on 100 parts by weight of the photocurable composition. Limiting the amount of the photoinitiator composition to the above range is advantageous for further improving the sensitivity, photocurability, development effect, and the like.
The photocuring composition can obtain better comprehensive performance when applied to a plurality of aspects of the photocuring field.
Still another aspect of the present application provides a photocurable product containing the above photocurable composition.
The photo-curing composition containing the photoinitiator and the free radical polymerizable compound also has better sensitivity, thermal stability, photo-curing efficiency and developing effect. Therefore, the light-cured product formed by the light-cured composition also has good comprehensive performance. Preferably, the above-mentioned photo-curable product includes an ink, a coating, an adhesive or a 3D imaging composition.
In addition to the photocurable composition, other components may be added to the adhesive according to the performance requirements of the adhesive. The above adhesive can be used for bonding glass, plastic, metal members, and the like. Furthermore, it is easy for those skilled in the art to add other necessary ingredients, such as one or more of stabilizers, surfactants, leveling agents, dispersing agents, as required by the prior art and the use of the photocurable composition.
The 3D image forming composition may contain other essential components in addition to the photocurable composition according to the performance requirements such as color of the ink and printing application. Preferably, the ink or coating and 3D printing formulation can be used for pattern printing, 3D printing, PCB solder mask, liquid or dry film resist material, substrate protective coating, and the like.
Yet another aspect of the present application also provides a photoresist comprising: the application provides the photoinitiator composition, the multifunctional acrylate monomer, the alkali-soluble resin and the solvent.
The photo-curing composition provided by the application also has better sensitivity, thermal stability, photo-curing efficiency and developing effect, so that the photoresist prepared by mixing the photoinitiator composition, the multifunctional acrylate monomer, the alkali-soluble resin and the solvent can also obtain better sensitivity, thermal stability, photo-curing effect and developing effect.
In order to further improve the comprehensive performance of the photoresist, the amount of the photoinitiator composition provided by the application is preferably 0.1 to 10 parts by weight, and more preferably 1 to 8 parts by weight, based on 100 parts by weight of the solid materials in the photoresist.
The multifunctional acrylate used in the photoresist may be selected from those commonly used in the art. In a preferred embodiment, the multifunctional acrylate includes, but is not limited to, dipentaerythritol hexaacrylate and/or pentaerythritol acrylate. The acrylates have higher functionality, so that the two acrylates are selected to further improve the photocuring performance of the photoresist.
In the developing process, the alkali-soluble resin in the photoresist reacts with alkali liquor to realize development, and the alkali-soluble resin can be selected from the types commonly used in the field. In a preferred embodiment, the alkali soluble resin includes, but is not limited to, polyacrylate having carboxylic acid group, more preferably copolymer obtained by copolymerizing methacrylic acid, itaconic acid or maleic acid with common monomers including, but not limited to, one or more of the group consisting of methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride in a desired ratio; the copolymer includes, but is not limited to, one or more of methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, or methyl methacrylate and butyl methacrylate and methacrylic acid and styrene copolymer.
In a preferred embodiment, the photoresist further comprises a pigment selected from one or more of a red pigment, a green pigment, and a blue pigment. For example, the pigment is selected from c.i. pigment red 177, c.i. pigment green 7, c.i. pigment blue 15:6, solvent blue 25. When the pigment in the colored photoresist is a well dispersed red pigment, green pigment or blue pigment, the colored photoresist becomes a colored photoresist. Color matrices can be fabricated using color photoresists for color display devices.
In a preferred embodiment, the photoresist further comprises a pigment, and the pigment is carbon black and/or titanium black. For example, the pigment is selected from carbon black, titanium black, c.i. pigment black 1. When the pigment in the above photoresist is a well dispersed black pigment such as carbon black or titanium black, it becomes a black photoresist. The black matrix, the spacer of the Cell gap, and the microlens can be manufactured using the black photoresist.
In a preferred embodiment, the above-described photoresist further comprises other photoinitiators or co-initiators, which are commercially available or known in the art, and which may be used as long as they are advantageous for the properties of the photocurable composition, particularly the photoresist. Such as Omnirad BDK, Omnirad 369, Omnirad 379, Omnirad 389, Omnirad TPO, Omnirad 819, Omnirad ITX, Omnirad DETX, Omnirad 784. Omnirad is a commercial product from IGM resin.
In addition to the above components, other resins such as one or more of the group consisting of polyalkylmethacrylate, ethyl cellulose, carboxymethyl cellulose, novolac resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide may be added.
In a preferred embodiment, any article obtained by coating, irradiating with light or other necessary processes such as development, postbaking, etc., using any material containing the photoinitiator composition of the present invention as a raw material, such as a finished product of a negative passivation film, a photocurable photosensitive surface coating, a barrier film, a polarizer coating, etc.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
A light source device:
365nm LED area light source, blue sky Tech lamp development Co.
Testing equipment:
stereoscopic microscope, COVS-50G, Mingmei photoelectricity technologies, Inc. Guangzhou.
Experimental materials:
comparative compound a 1: from compound preparation 3;
comparative compound a 2: from compound preparation 4;
compounds of formula I-30: from compound preparation 1;
a compound of formula II-1: from compound preparation 5;
a compound of formula II-3: from compound preparation 6;
a compound of formula II-5: from compound preparation 2;
omnirad DETX: photoinitiator products from IGM resins;
esacure 3644: photoinitiator products from IGM resins;
omnirad EMK: photoinitiator products from IGM resins;
OXE 01: a compound of formula III-1, a photoinitiator product of BASF;
PBG 305: a compound of formula III-4, a product of Changzhou powerful new electronic materials GmbH;
PBG 3057: a compound of formula III-6, a product of Changzhou powerful new electronic materials GmbH;
SPI 02 Compound of formula III-33, a product of Samyong, Korea;
a compound of formula III-15 from preparation 7;
photomer 6010: aliphatic polyurethane triacrylate, product of IGM resins, Netherlands;
DPHA: dipentaerythritol penta-and hexa-acrylate, a product of Tianjin Tianjiao chemical Co.
Preparation examples
Compound preparation example 19-preparation of ethyl-3, 6-bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl ] carbazole (compound of formula i-30)
1 a.9-ethyl-3, 6-bis (4-fluorobenzoyl) carbazole
Adding 19.5g of N-ethyl carbazole into 250ml of dichloroethane for dissolving, then adding 34g of aluminum trichloride, keeping the temperature between 0 ℃ and-5 ℃, dropwise adding 40g of p-fluorobenzoyl chloride into the solution, and then keeping the reaction liquid at the temperature between 0 ℃ and 5 ℃ for reacting for 15 hours. The reaction mixture was added in portions to 100ml of 10% HCl solution at 0 ℃ and stirred for 30 min. After standing for 30 minutes, the phases were separated and the dichloroethane phase was washed with 50ml of 2% sodium hydroxide solution for 30 minutes, the dichloroethane phase being separated off. The dichloroethane solution was distilled under reduced pressure and dichloroethane was recovered, and 80ml of ethyl acetate was added to the residue to crystallize it, giving 30.5g of the product, 98.5% in the form of white powder, and 69.5% in yield.
1 b.9-Ethyl-3, 6-bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl ] carbazole
30g of 9-ethyl-3, 6-bis (4-fluorobenzoyl) carbazole, 25g of 2,2,3, 3-tetrafluoropropanol and 8g of sodium hydroxide are dissolved in 200ml of pyridine and reacted at 70 ℃ for 18 h. Distilling under reduced pressure to remove pyridine and redundant 2,2,3, 3-tetrafluoropropanol. 100ml of water and 250ml of dichloroethane were added to the residue and stirred for 1 hour. The aqueous phase is separated and the dichloroethane solution is washed 2 times with 100ml of water. Distilling under reduced pressure to recover dichloroethane, adding 150ml of ethyl acetate and 2g of activated carbon to the residue, heating and refluxing for 1 hour, filtering the activated carbon, distilling the filtrate under reduced pressure to remove about 100ml of ethyl acetate, cooling to crystallize, filtering, and drying the filter cake to obtain 27.8g of light yellow powder with the content of 98.5% and the yield of 61.4%.
Warp beam1H-NMR(CDCl3) Confirmation of the structure, delta [ ppm ]]:1.512(t,3H)，4.425-4.483(m,6H)，5.949-6.277(m,2H)，7.016-7.045(m,4H)，7.496-7.517(d,2H)，7.844-7.868(d,4H)，7.990-8.011(d,2H)，8.534(s,2H)。
Compound preparation example 211- (2-ethylhexyl) -5, 8-bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl ] -11H-benzo [ a ] carbazole (Compound of formula II-5) preparation
2a.11- (2-ethylhexyl) -5, 8-bis (4-fluorobenzoyl) -11H-benzo [ a ] carbazole
A50 ml single neck flask was charged with B03D 2.0.0 g, dichloroethane 20ml was added and dissolved, and zinc chloride 0.2g and o-fluorobenzoyl chloride 2.3g were added and the reaction was stirred at 80 ℃ for 10 hours. After cooling, the reaction solution was washed twice with 20ml of water, and the dichloroethane solution was concentrated to dryness under reduced pressure to give 4.0g of a brown viscous substance which was used in the reaction of 2b without purification.
2b.11- (2-ethylhexyl) -5, 8-bis [4- (2,2,3, 3-tetrafluoropropoxy) benzoyl ] -11H-benzo [ a ] carbazole
4.0g of the product 11- (2-ethylhexyl) -5, 8-bis (4-fluorobenzoyl) -11H-benzo [ a ] carbazole of 2a was dissolved in 20ml of pyridine in a 50ml single-neck flask, and 2.2g of tetrafluoropropanol and 1.2g of sodium hydroxide were added thereto, and the mixture was stirred at 80 ℃ for 5 hours. The reaction solution was added dropwise to 100ml of water, followed by stirring with 100ml of dichloroethane for 1 hour and then standing for separation. The separated dichloroethane solution was concentrated to dryness under reduced pressure to give 4.7g of a coffee-colored solid. The solid is heated and dissolved by using a mixed solvent of 20ml of ethyl acetate and 20ml of ethanol, 0.25g of activated carbon is added for refluxing for 1 hour, the mixture is thermally filtered, yellow crystals are separated out after the temperature of the filtrate is reduced, 2.5g of the yellow crystals are weighed after drying, and the total yield of the two steps is 51.3 percent, and the content is 98.51 percent.
Warp beam1H-NMR(CDCl3) Confirmation of the structure, delta [ ppm ]]:0.754-0.789(m,6H)，1.126-1.328(m,8H)，2.113(s,1H)，4.369-4.452(t,2H)，4.513-4.599(t,2H)，4.928(m,2H)，4.994-5.342(m,1H)，5.537-5.885(m,1H)，7.251-7.272(m,4H)，7.430-7.455(d,1H)，7.566-7.811(m,6H)，7.950-7.979(d,1H)，8.430(s,1H)，8.571(s,1H)，8.668-8.695(d,1H)，8.736-8.764(d,1H)。
Compound preparation example 33- (2-methylbenzoyl) -9-ethylcarbazole preparation (comparative compound a1)
Reference is made to the description of patent CN100528838C, page 81, operation 1.a of example 1, replacing benzoyl chloride with o-methylbenzoyl chloride, to 40ml CH2Cl27.83g (40.1mmol) of N-ethylcarbazole in (1) was added with 5.88g (44.1mmol) of AlCl3Maintaining the temperature below 10 ℃, dropwise adding 6.5g (42mmol) of o-methylbenzoyl chloride, stirring at room temperature for 4 hours, dropwise adding the reaction mixture into ice water containing hydrochloric acid, separating an organic phase, washing with water to neutrality, and performing anhydrous MgSO (MgSO) treatment4The organic phase was dried and then purified on a silica gel column with dichloromethane-n-hexane (1: 1) to give 9.45g of a white solid with a yield of 75.1% and a content of 98.51%.
Warp beam1H-NMR(CDCl3) Confirmation of the structure, delta [ ppm ]]:1.431/1.455/1.479(t,3H),2.349(s,3H),4.352/4.376/4.400/4.424(quartet,2H),7.246-7.530(m,8H),7.989/7.994/8.018/8.023(dd,1H),8.065/8.090(d,1H),8.561/8.564(d,1H)。
Preparation of Compound 43, 6-bis (2-methylbenzoyl) -9- (3-methylbutyl) carbazole (comparative Compound A2)
4.5g (19mmol) of N- (3-methylbutyl) carbazole are dissolved in 20ml of 1, 2-dichloroethane, the temperature is reduced to-5 ℃ in a low-temperature bath, 5.3g (40mmol) of anhydrous aluminum trichloride is added, a solution of 6.0g (38.8mmol) of o-methylbenzoyl chloride and 10g of dichloroethane is added dropwise, and the reaction is carried out for 3h while keeping the temperature at 5 ℃. Dropping the reaction solution into 20ml concentrated hydrochloric acid and 40ml water at the temperature of not more than 10 ℃, stirring 30mim, standing for layering, and washing the separated organic phase to be neutral by 80ml water. Dichloroethane was concentrated under reduced pressure to give 10.0g of a pale yellow glass; adding 150ml of absolute ethyl alcohol, heating and refluxing, dissolving completely, cooling to separate out crystals, filtering, and drying a filter cake to obtain 8.0g of white powder, wherein the HPLC analysis content is 98.53%, and the yield is 96.4%.
By 1H-NMR (CDCl)3) Confirmation of the structure, delta [ ppm ]]:1.031/1.052(d,6H),1.681-1.815(m,3H),2.344(s,6H),4.347/4.374/4.397(t,2H),7.289-7.467(m,10H),8.018/8.023/8.047/8.052(dd,2H),8.535/8.540(s,2H)。
Preparation of Compound 55- (2,4, 6-trimethylbenzoyl) -11- (2-ethylhexyl) -11H-benzo [ a ] carbazole (Compound of formula II-1)
Reference is made to the partial procedure of 18.a in example 18 on page 63 of the specification of patent CN103153952A, in a 1L reactor flask, with 400ml of CH2Cl247.16g (143.0mmol) of 11- (2-ethylhexyl) -11H-benzo [ a ] are dissolved therein]Carbazole, 20.0g (150mmol) AlCl was added327.45g (150mmol) of 2,4, 6-trimethylbenzoyl chloride was added dropwise to the solution while maintaining the temperature at 0 ℃ and then stirred at room temperature for 2 hours, the reaction mixture was poured into ice water, and CH was separated2Cl2Solution phase, continued with CH2Cl2Extracting the aqueous phase twice, combining the organic phases, washing to neutrality with water, MgSO4Drying and concentrating most of CH2Cl2Then, 230ml of n-hexane was added to precipitate a beige solid, which was dried under reduced pressure and weighed 65.0g, the content of which was 99.1%, the yield was 95.6%, and the structure was confirmed to be 5- (2,4, 6-trimethylbenzoyl) -11- (2-ethylhexyl) -11H-benzo [ a ] by 1H-NMR spectroscopy]Carbazole.
By 1H-NMR (CDCl)3) Confirmation of the structure, delta [ ppm, CDCl3]:0.805/0.823/0.841(t,3H),0.872/0.891/0.909(t,3H),1.184-1.408(m,9H),2.198(s,6H),2.390(s,3H),4.670-4.785(m,2H),6.946(s,2H),7.271/7.288(d,1H),7.450/7.453//7.471/7.474//7.489/7.491(dt,1H),7.550/7.571(d,1H),7.667/7.670//7.684/7.687/7.691//7.705/7.709(dt,1H),7.720/7.724//7.738/7.742/7.746//7.759/7.762(dt,1H),7.939/7.958(d,1H),8.361(s,1H),8.643/8.662(d.2H),9.629/9.632//9.650/9.653(dd,1H)。
Preparation of Compound 65- (2,4, 6-trimethylbenzoyl) -8- [2- (2,2,3, 3-tetrafluoropropoxy) benzoyl ] -11- (2-ethylhexyl) -11H-benzo [ a ] carbazole (Compound of formula II-3)
With reference to the partial procedure of patent CN103153952A description, pages 63-64, example 18, 18.a and 18.b, etherification was carried out with 2,2,3, 3-tetrafluoro-1-propanol instead of 2-methoxyethanol, and the etherification product was extracted to give a beige solid by1The structure of 5- (2,4, 6-trimethylbenzoyl) -8- [2- (2,2,3, 3-tetrafluoropropoxy) benzoyl is confirmed by H-NMR spectroscopy]-11- (2-ethylhexyl) -11H-benzo [ a]Carbazole.
By 1H-NMR (CDCl)3) Confirmation of the structure, delta [ ppm, CDCl3]:0.795/0.819/0.843/0.870/0.894(dt,6H),1.170-1.465(m,9H),2.189(s,6H)；2.398(s,3H),4.243/4.281/4.318(t,2H),4.660-4.817(m,2H),5.072/5.091/5.110//5.249/5.267/5.286//5.425/5.444/5.463(tt,1H),6.958(s,2H),6.958/6.989(d,1H),7.158/7.183/7.207(t,1H),7.456-7.549(m,3H),6.682-7.795(m,3H),8.362(s,1H),8.607/8.611(d,1H),8.621/8.649(d.1H),9.540/9.544//9.568/9.572(dd,1H)。
Compound preparation example 74, 4' -bis (2-acetoxyiminopropionyl) diphenyl sulfide (Compound of formula III-15)
Preparation of 4, 4' -Diproyl diphenyl sulfide
Weighing 79.0g (0.424mol) of diphenyl sulfide, dissolving the diphenyl sulfide in 600g of 1, 2-dichloroethane, adding 124.4g (0.933mol) of anhydrous aluminum trichloride, stirring and cooling to 0 ℃; keeping the temperature below 5 ℃, dropwise adding 82.4g (0.891mol) of propionyl chloride, after finishing dropwise adding for 2h, keeping the temperature below 0 ℃ and stirring for 2 h; dropwise adding the reaction solution into 450ml of 10% diluted hydrochloric acid, controlling the temperature of the acid solution to be not higher than 30 ℃, stirring for 1h after the addition is finished, and separating a lower organic phase; the organic phase is washed three times by 300ml of water in sequence; the organic phase is subjected to reduced pressure distillation to recover the solvent, and 126g of residues are obtained; adding 240ml of n-hexane while the solution is hot, and keeping the temperature to clarify the solution; naturally cooling to crystallize, and cooling the crystallization bottle to 0 deg.C when the temperature of the solution is lower than 30 deg.C; suction filtering to obtainDrying the white filter cake at 50 ℃ under reduced pressure to obtain 117.6g of white crystals with the yield of 93 percent and the HPLC analysis purity of 98.5 percent, the melting range of 123.1-130.3 ℃,1H-NMR data show that the obtained product is 4, 4' -dipropionyl diphenyl sulfide.
Preparation of 4, 4' -bis (2-hydroxyiminopropionyl) diphenyl sulfide
Taking 30g (0.1mol) of 4, 4' -dipropionyl diphenyl sulfide obtained in 7a, dissolving the product in 100g of dimethyl sulfoxide, adding 3.0g of 36% concentrated hydrochloric acid, stirring in a water bath at the temperature of 20-25 ℃, dropwise adding 25g (0.24mol) of n-butyl nitrite within 30min, and stirring for 10 h; dropwise adding the reaction solution into 1L of ice water, precipitating light yellow solid, performing suction filtration, drying under reduced pressure, weighing 27g, and analyzing by HPLC (high performance liquid chromatography) to obtain 97.80% purity and 75% yield; the melting range is between 162.8 and 169.5 ℃,1the H-NMR data showed that the product was 4, 4' -bis (2-hydroxyiminopropionyl) diphenyl sulfide. Delta (CDCl)3Ppm) value data of 2.022(s,6H,2CH3), 7.425/7.452(d,4H,4ArH), 7.823/7.851(d,4H,4ArH), 12.450(s,2H,2 NOH).
Preparation of 4, 4' -bis (2-acetoxyiminopropionyl) diphenyl sulfide
Adding 24.5g (0.068mol) of 7b product 4, 4' -bis (2-hydroxyiminopropionyl) diphenyl sulfide and 150ml of toluene into a reaction bottle, placing the reaction bottle in a water bath at 20-25 ℃, dropwise adding 19.6g (0.19mol) of acetic anhydride into the reaction bottle through a constant-pressure dropping funnel, and stirring for 6 hours; adding 100ml of water into the reaction solution, and stirring for 30 min; washing the toluene phase with 100ml of 1% sodium bicarbonate solution, 50ml of water and 50ml of water in sequence; filtering the toluene solution, and carrying out reduced pressure distillation to recover toluene to obtain 28.5g of a yellow solid crude product; adding 55ml of hot ethyl acetate to dissolve the solid, then adding 85ml of hot n-hexane, naturally cooling to separate out crystals, carrying out suction filtration, and drying a filter cake in vacuum to obtain 27.2g of a light yellow solid crystal product, wherein the HPLC analysis content is 99.2%, and the yield is 90.8%; the melting range is 108.0-111.5 ℃;1H-NMR(CDCl3) δ (ppm) value data: 2.274(s,6H,2 CH)3),2.293(s,6H,2COCH3),7.417/7.445(d,4H,4ArH),8.050/8.078(d,4H,4ArH)。
Preparation of the photoinitiator composition
Composition preparation example 1:
12g of the compound shown in the formula II-5 and 28g of an OXE 01 sample are put into a mortar for grinding and mixing to obtain 40g of a composition, and the molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.24: 1.
Composition preparation example 2:
taking 12g of the compound shown in the formula I-30 and 28g of the compound shown in the formula III-4, putting into a mortar, grinding and mixing to obtain 40g of the composition, wherein the molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.29: 1.
Composition preparation example 3:
12g of the compound shown as the formula II-1 and 28g of an OXE 01 sample are put into a mortar for grinding and mixing to obtain 40g of a composition, and the molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.40: 1.
Composition preparation example 4:
taking 12g of the compound shown in the formula I-30 and 12g of the compound shown in the formula III-6, putting the mixture into a mortar, grinding and mixing to obtain 24g of the composition, wherein the molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.6: 1.
Composition preparation example 5:
taking 12g of the compound shown in the formula II-5 and 28g of the compound shown in the formula III-33, putting into a mortar, grinding and mixing to obtain 40g of the composition, wherein the molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.23: 1.
Composition preparation example 6:
taking 12g of the compound shown in the formula I-30 and 12g of the compound shown in the formula III-33, putting the mixture into a mortar, grinding and mixing to obtain 24g of the composition, wherein the molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.64: 1.
Alkali soluble resin preparation
18g of benzyl methacrylate, 6g of methacrylic acid, 6g of hydroxyethyl methacrylate, 1.5g of azobisisobutyronitrile, 0.6g of dodecanethiol and 200ml of toluene are put into a constant-pressure dropping funnel for 1L, 100ml of toluene is put into a 500ml four-mouth bottle, nitrogen is replaced, the temperature is increased to 80 ℃, the solution in the funnel is dropped, and after 6 hours of reaction, the solution is cooled and filtered, so that 24g of white alkali-soluble resin is obtained.
Preparation of black color paste
50g of alkali-soluble resin, 50g P25 g of carbon black, 100g of DPHA and 250g of propylene glycol methyl ether acetate are put into a 500ml beaker and mixed for 15min at the rotating speed of 3000r/min by a high-speed shearing mixer to prepare black color paste.
Photoresist examples 1-13 and comparative examples 1-14
Each example and each comparative example were prepared in the weight ratio of each component described in tables 1 to 5. The initiator (oxime ester compound) and the sensitizer (acylcarbazole derivative) can be used in the composition preparation example or mixed according to the proportion in the table and dissolved in PMA, and then the composition solution is mixed with the black color paste according to the proportion. The components are uniformly mixed, a 10-micron wire rod is used for coating a film on a glass slide, the film is dried for 5min in a 90-DEG C oven, a 365-nm light source is used for matching with a mask plate for curing, 1% NaOH solution is used for developing at 25 ℃, purified water is used for soaking and cleaning for 10s, and the line width of a developed image is measured after the film is dried for 30min in the 90-DEG C oven.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
| Example 10 | Example 11 | Example 12 | Comparative example 15 | Comparative example 16 | |
| Compounds of formula III-4 | 0.056 | 0.028 | 0 | 0.08 | 0 |
| Compounds of formula III-33 | 0 | 0 | 0.056 | 0 | 0.08 |
| Compounds of formula I-30 | 0.024 | 0.052 | 0.024 | 0 | 0 |
| PMA | 2 | 2 | 2 | 2 | 2 |
| Black color paste | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 |
| Sensitizer/initiator molar ratio | 0.29 | 1.26 | 0.27 | 0 | 0 |
The examples and comparative examples in table 1 were coated, cured, developed, and measured, and the data are shown in table 6, and the results show: when OXE 01 is used as an initiator and the compound represented by the formula I-30 is used as a sensitizer, the developed line width value of the examples in which the use ratio is within the range required by the present invention is significantly larger than that of the corresponding comparative examples, and the sensitivity is significantly higher than that of the comparative examples in which no sensitizer is used, the sensitizer is used alone or the amount of the sensitizer is outside the range required by the present invention, particularly the results of comparative example 3 show that the compound represented by the formula II-1 alone has no polymerization initiating effect.
TABLE 6
| Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Development Point/s | 20 | 20 | 20 | 20 | 15 | 19 |
| 120 μm line width/μm | 129 | 134 | 123 | 95 | 0 | 116 |
The examples and comparative examples in table 2 were coated, cured, developed, measured, and the test result data are shown in table 7, and the results show: in the case of using PBG 3057 as an initiator and the compounds represented by the formulas I to 30 as sensitizers, the developed line width values of the examples in which the use ratios thereof were within the range required by the present invention were significantly larger than those of the corresponding comparative examples, and the sensitivity was significantly higher than that of the comparative examples in which no sensitizer was used, in which the sensitizer was used alone or in which the amount of sensitizer was outside the range required by the present invention.
TABLE 7
| Example 3 | Example 4 | Example 5 | Comparative example 5 | Comparative example 3 | Comparative example 6 | |
| Development Point/s | 20 | 20 | 20 | 20 | 20 | 20 |
| 120 μm line width/μm | 147 | 132 | 140 | 129 | 0 | 126 |
The examples and comparative examples in Table 3 were coated, cured, developed and measured, and the data of the results are shown in Table 8, which shows that in the case of using the compounds of the formulae III to 15 as the initiator and the compounds of the formulae I to 30 as the sensitizer, the developed line width values of the examples in the ratio within the range required by the present invention were significantly larger than those of the corresponding comparative examples, and the sensitivity was significantly higher than that of the comparative examples in which no sensitizer was used or the amount of sensitizer was outside the range required by the present invention.
TABLE 8
| Example 6 | Example 7 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | |
| Development Point/s | 20 | 20 | 20 | 20 | 20 | 20 |
| 120 μm line width/μm | 136 | 135 | 129 | 108 | 110 | 105 |
The examples and comparative examples in Table 4 were coated, cured, developed and measured, and the data of the results are shown in Table 9, which shows that the cured and developed line width values are significantly higher than those of the corresponding comparative examples using PBG 3057 as an initiator and the compound represented by formula I-30, the compound represented by formula II-1 or the compound represented by formula II-5 as a sensitizer, and the sensitivity is significantly higher than those of the comparative examples without sensitizer and those with Esacure 3644, Omnirad DETX, Omnirad EMK sensitization.
TABLE 9
Table 5 and comparative examples were coated, cured, developed and measured, and the results of the test data shown in Table 10 show that when SPI 02, PBG 305 were used as the initiator and the compound of formula I-30 was used as the sensitizer, the cured and developed line width values were significantly greater than those of the corresponding comparative examples, and the sensitivity was significantly higher than that of the comparative examples without the sensitizer.
Watch 10
| Example 10 | Example 11 | Example 12 | Comparative example 15 | Comparative example 16 | |
| Development Point/s | 32 | 33 | 25 | 30 | 22 |
| 120 μm line width/μm | 140 | 133 | 148 | 128 | 130 |
Adhesives example 13, example 14 and comparative example 17
Each example and comparative example were prepared according to the weight parts of each component in table 11, and after the components were uniformly mixed, a 50 μm wire bar was used to coat a film on a glass slide, a 365nm light source was used in conjunction with a mask plate to perform curing, the film weight was measured after curing, and then the film weight was measured again after being soaked in acetone at room temperature for 36 hours, and the gel conversion rate was calculated.
TABLE 11
| Example 13 | Example 14 | Comparative example 17 | |
| Photomer 6010 | 5 | 5 | 5 |
| HPMA | 4.5 | 4.5 | 4.5 |
| OXE 01 | 0 | 0 | 0.5 |
| Composition preparation example 1 | 0.5 | 0 | 0 |
| Composition preparation example 2 | 0 | 0.5 | 0 |
The test data of comparative examples and examples in table 11 are shown in table 12. As can be seen from the data, the adhesive photogel conversion of examples 13 and 14 using the photocurable compositions provided by the present invention is significantly higher than that of comparative example 17 using the oxime ester photoinitiator alone.
TABLE 12
| Example 13 | Example 14 | Comparative example 17 | |
| Gel conversion rate,% of | 92.3 | 92.1 | 85.2 |
In conclusion, the curing activity of the photoinitiator composition containing the acylcarbazole derivative and the oxime ester in the photocuring composition is remarkably higher than that of the photoinitiator composition using the same oxime ester alone, when the molar ratio of the acylcarbazole derivative to the oxime ester is 0.2: 1-1: 1, the best sensitization effect is shown, and particularly, the fluoroalkyl-containing compound is remarkably superior to a comparative compound.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: in the photoinitiator, the acylcarbazole derivative with a specific structure and the oxime ester compound are matched for use, and the initiator has excellent sensitivity and thermal stability through the synergistic effect of the acylcarbazole derivative and the oxime ester compound, and simultaneously, the photocuring efficiency and the developing effect of the photoinitiator can be greatly improved.
It is 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 elements 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 or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (18)
1.A photoinitiator composition, comprising: acylcarbazole derivatives and oxime ester compounds; wherein
The acylcarbazole derivative is one or more selected from the group consisting of a compound represented by formula I, a compound represented by formula II-A, a compound represented by formula II-B, a compound represented by formula II-C, a compound represented by formula II-D, a compound represented by formula II-E, a compound represented by formula II-F, a compound represented by formula II-G, a compound represented by formula II-H and a compound represented by formula II-I;
the oxime ester compound is a compound shown as a formula (III);
wherein R is1，R2，R4，R5，R7，R8，R24，R25，R27，R28，R34，R35，R37，R38，R41，R42，R44，R45，R47，R48，R54，R55，R61，R62，R67，R68，R71，R72，R74，R75，R102-R108，R112，R114，R115，R117，R118，R121，R122，R124-R127Each independently being H, a halogen atom, C1-C8Alkyl radical, C1-C8Alkoxy, CN;
R70is selected from H or C1-C10Alkoxy radical, R73Selected from H, C6-C20Aroyl radical of said C6-C20At least one hydrogen atom in aroyl group being substituted by a halogen atom, and/or at said C6-C20A substituent formed by inserting an O atom into the side chain of the aroyl;
R6，R26，R36，R46，R56，R66，R106，R116each independently selected from H, halogen atom, CN, C1-C8Alkyl radical, C1-C12Alkyl acyl radical, C5-C6Substituted C1-C3Alkyl acyl radical, C6-C20Aroyl radical, C4-C20(ii) a heteroaryl acyl group,
or said R6Said R is26Said R is36Said R is46Said R is56Said R is66Said R is106Said R is116Respectively form a 5-7 membered ring with adjacent substituent groups, wherein C6-C20Aroyl with said C4-C20Substituents on the heteroaroyl group include halogen atoms, R40、OR50、SR50、NR51R52、COOR50Or CONR51R52；
When said R is116Is C6-C20Aroyl or C4-C20In the case of heteroarylacyl, the ortho-substituent of the acyl group on the aromatic or heteroaromatic ring is attached to any carbon atom on the carbazole ring;
R9，R29，R39，R49，R59，R69each independently selected from C1-C12Straight or branched alkyl, C2-C12Alkenyl radical, C3-C12Alkenylalkyl, or C1-C12Straight or branched alkyl, C2-C12Alkenyl radical, C3-C12A first group formed by substitution of a hydrogen in an alkenylalkyl group with one or more of the following substituents: phenyl radical, C5-C6Cycloalkyl radical, C3-C6Heterocyclyl, halogen, COOR20、OR20、SR20、PO(OCnH2n+1)2、Si(CnH2n+1)3N is an integer of 1 to 4; or
The R is9Said R is29Said R is39Said R is49Said R is59Said R is69Each independently selected from C3-C12Alkyl and/or C3-C12Alkenylalkyl with one or more O, S, SO insertions in the carbon chain2CO or COO; or said R9Said R is29Said R is39Said R is49Said R is59Said R is69Each independently selected from C2-C12Alkylene and/or C4-C12Alkylene containing a double bond, and said C2-C12Alkylene or C4-C12A group linked to the double bond-containing alkylene terminal and said R9Said R is29Said R is39Said R is49Said R is59Said R is69The groups to which each is attached are the same; or
The R is9Said R is29Said R is39Said R is49Said R is59Said R is69Each independently selected from phenyl, or a second group formed by phenyl substituted with one or more of the following substituents: c1-C8Alkyl, halogen atom, OR20、SR20、COR30、CN、COOH；
R10，R110，R120，R130Each independently selected from C1-C12Alkyl or C6-C20An aryl group;
Ar1，Ar2，Ar3，Ar4，Ar5，Ar6，Ar7，Ar8，Ar9each independently selected from C6-C20Aryl radical, C4-C20Heteroaryl, or said C6-C20Aryl and said C4-C20At least one H on the heteroaromatic group is substituted with a group formed by: halogen atom, CN, R40，OR50，SR50，NR51R52，COOR50，CONR51R52Wherein Ar is1Ar is said2Ar is said5The ortho position of the acyl group can be connected with any carbon atom on the carbazole ring through O and S atoms, and the Ar1Phenyl, o-methylphenyl and p-methylphenyl are excluded;
y is selected from C1-C3A linear or branched alkylene group; m, n are each independently selected from 0 or 1;
in the formula (III), Ar9A third group selected from those having the parent structure arylthioaryl, fluoren-2-yl, benzofluorenyl or coumarin-3-yl, or groups in which hydrogen is substituted by one or more of the following substituents: halogen atom, nitro group, R11A or
The substitution is carried out by the following steps,
m is1Is 0 or 1;
a is selected from a direct bond, O, S, CO or R11' N, and said R11' is C1-C12An alkyl group;
the R is11Is selected from C1～C12Alkyl, C interrupted by one or more oxygen or sulfur atoms3～C12Alkyl radical, C3～C8Cycloalkyl of, C3～C8Heterocyclic group, C2～C7Alkenylmethyl, C6～C15Aryl or C4～C15Heteroaryl, and said C6～C15Aryl and C4～C15The hydrogen atoms in the heteroaryl groups may be replaced by fluorine atoms, or C1-C4Alkylsulfonyl substituted, and said C1～C4The hydrogen atom of the alkyl group may be replaced by F, C1-C4Alkoxy, OH, OOCR14、COOR19、(R19O)2P(O)、(CH3)3Si or phenyl, said R19Is C1-C4An alkyl group; or said R11Or said R11' form a 5-7 membered ring with the atom on the adjacent parent, or R11R11' N is a cyclic substituent; or
Ar is9Form a 5-7 membered ring with an adjacent substituent;
the R is13Is C1-C16Alkyl, phenyl, C4-C7Cycloalkyl radical, C1-C16Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO or R40Radicals formed by OOC substitution, C3-C16Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO or R40OOC substituted and interrupted by at least one oxygen or sulfur atom, or phenyl hydrogen atoms interrupted by at least one halogen atom, C1-C12Alkyl radical, C1-C4Alkoxy, CN substituted group, or said R13To adjacent Ar9Joined to form a 5 to 7 membered ring, said R14Is selected from C1-C11Alkyl radical, C3-C5Alkenyl radical, C1-C4Alkoxy, phenoxy, phenyl, C1-C11Hydrogen atoms in alkyl radicals being bound by at least one halogen atom, C4-C7A group formed by substituting cycloalkyl or CN, or a group formed by substituting hydrogen atom in phenyl with at least one halogen atom, C1-C4Alkyl radical, C1-C4Alkoxy and CN;
the R is20And said R30Each independently selected from H, C1-C8Alkyl through one or more of F, Cl, OH, C5-C6C formed by substitution of cycloalkyl1-C8Alkyl, containing one or more O or S spacers, and interrupted by hydroxy and/or OOCR4Substituted C3-C8Alkyl, five-or six-membered rings containing one or 2 heteroatoms O, S, N, phenyl, via one or more halogen atoms or C1-C4Alkyl-substituted phenyl;
the R is40And said R50Each independently selected from C1-C8Alkyl radical, C1-C8Radicals formed by substitution of alkyl radicals by at least one F, Cl or hydroxy radical, C3-C8Radicals formed by insertion of one or more oxygen atoms in the alkyl radical and substitution of at least one hydrogen atom by a hydroxyl and/or acetoxy radical, five-or six-membered rings containing 1-2 heteroatoms, phenyl, or C1-C4An alkyl phenyl group;
the R is51And said R52Each independently selected from C1-C4Alkyl, C substituted by hydroxy1-C4Alkyl, or NR51R52Is a cyclic substituent.
2. The photoinitiator composition according to claim 1 wherein the compound of formula i is selected from one or more compounds of formulae (i-1) to (i-36):
3. the photoinitiator composition of claim 1 wherein the compounds of formulae II-A, II-B, II-C, II-D, II-E, II-F, II-G and II-H are selected from one or more of the following organic compounds:
4. the photoinitiator composition according to claim 1 wherein the oxime ester compound of formula iii is selected from one or more of the following compounds:
wherein, Y1，Y2Each independently is H, C1-C12Alkyl, nitro, Ar10CO or
m2，n1，n2Each independently is 1 or 0;
Ar10is C6-C15Aryl or C4-C15Heteroaryl, in which hydrogen on carbon is optionally replaced by fluorine atom, C1-C4Alkyl radical, C1-C4Alkoxy radical, C1-C4Alkylthio radical, C1-C4Alkylsulfonyl substituted, and C1-C4Hydrogen in the alkyl radical being bound by fluorine atoms, C1-C4Alkoxy or R14COO substitution;
R17，R18each independently is H, C1-C8Alkyl, C interrupted by one or 2 oxygen atoms3-C8Alkyl radical, C2-C7Alkenylmethyl, phenyl; hydrogen of alkyl and phenyl optionally substituted by halogen atoms, C4-C7Cycloalkyl, hydroxy, R14COO、COOR19、(R19O)2P(O)、(CH3)3Si and phenyl substitution; r19Is C1-C4Alkyl, or R17，R18Each independently may form a 5 to 7 membered ring with the adjacent substituents and atoms on the parent;
R15，R16，R21，R22，R71，R72，R73，R74，R75each independently is H, C1-C8Alkyl radical, C1-C8Alkoxy group, halogen atom, CN,
C6-C15Aromatic acyl radical, C4-C15Heteroaromatic acyl group, the C1-C8Hydrogen in alkyl by one or more halogen atoms, C4-C7Cycloalkyl, hydroxy, CN, R14COO-substituted substituent, C6-C15Aryl and/or C4-C15A group formed by substituting hydrogen on a heteroaryl group with one or more of the following: H. halogen atom, CN, R40、OR50、SR50、NR51R52、COOR50Or CONR51R52Or adjacent substituents may form a 5 to 7 membered ring;
R13' is C1-C16Alkyl, phenyl, C4-C7Cycloalkyl radical, C1-C16Hydrogen in the alkyl radical being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R14COO for the radical formed, C3-C16Hydrogen in the alkyl radical being bound by at least one halogen atom, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, a group substituted by hydroxy and/or interrupted by at least one oxygen or sulphur atom, the hydrogen of the phenyl group being interrupted by at least one halogen atom, C1-C12Alkyl radical, C1-C4Alkoxy and CN; r13Is' a C1-C16Alkyl radicals, substituted by one or more halogen atoms, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy, CN, R4COO、R20OOC substituted C1-C16Alkyl radicals, substituted by one or more halogen atoms, C4-C7Cycloalkyl radical, C4-C7Heterocyclyl, phenyl, hydroxy-substituted C interrupted by one or more oxygen, sulfur atoms3-C16Alkyl, phenyl, substituted by one or more halogen atoms, C1-C12Alkyl radical, C1-C4Alkoxy, CN-substituted phenyl, C4-C7A cycloalkyl group; or R13' may be linked to an adjacent benzene ring to form a 5-to 7-membered five-to seven-membered ring;
the R is40Said R is50Each independently selected from H, C1-C8Alkyl radical, C1-C8The hydrogen in the alkyl group being reacted with one or more of F, Cl, OH, C3-C7Radicals formed by cycloalkyl substitution, C3-C8Alkyl interrupted by one or more O and/or S, and hydrogen interrupted by hydroxy and/or OOCR4Radicals formed by substitution, five-or six-membered rings containing one or two heteroatoms O, S, N, benzeneRadical, or C1-C4An alkyl phenyl group;
the R is51Said R is52Each independently selected from C1-C4Alkyl, C substituted by hydroxy1-C4An alkyl group; or the NR51R52Is selected from
5. The photoinitiator composition according to claim 4, wherein the oxime ester compound of formula III is selected from one or more of the following compounds:
6. the photoinitiator composition according to claim 1, wherein the molar ratio of the acylcarbazole derivative to the oxime ester compound is (0.1-1.4): 1;
preferably, the molar ratio of the acylcarbazole derivative to the oxime ester compound is (0.2-1): 1.
7. A photocurable composition comprising a photoinitiator and a radically polymerizable compound, characterized in that the photoinitiator comprises a photoinitiator composition according to any one of claims 1 to 6.
8. The photocurable composition of claim 7 wherein the free-radically polymerizable compound is selected from one or more of the group consisting of acrylate compounds, methacrylate compounds, and acrylate or methacrylate group containing resins.
9. The photocurable composition according to claim 7 or 8, wherein the photoinitiator composition according to any one of claims 1 to 6 is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photocurable composition;
preferably, the photoinitiator composition according to any one of claims 1 to 6 is used in an amount of 1 to 8 parts by weight based on 100 parts by weight of the photocurable composition.
10. A photocurable product comprising the photocurable composition according to any one of claims 7 to 9.
11. The photocurable composition of claim 10 wherein the photocurable product comprises an ink, coating, adhesive, or 3D imaging composition.
12. A photoresist, wherein the photoresist comprises:
the photoinitiator composition of any one of claims 1 to 6, a multifunctional acrylate monomer, an alkali soluble resin, and a solvent.
13. The photoresist of claim 12, further comprising a pigment selected from one or more of a red pigment, a green pigment, and a blue pigment.
14. The photoresist of claim 12, further comprising a pigment selected from carbon black and/or titanium black.
15. A color matrix fabricated using the photoresist of claim 13.
16. A black matrix, which is produced by using the resist according to claim 14.
17. An optical spacer produced by using the resist according to claim 14.
18.A color filter device, wherein the color filter device is prepared from the photoresist of any one of claims 12 to 14.
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| CN116410227A (en) * | 2023-04-03 | 2023-07-11 | 上海辉纳思光电科技有限公司 | Phosphonic acid derivative of carbazole, quantum dot light emitting device and perovskite solar cell |
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| CN116410227B (en) * | 2023-04-03 | 2024-05-14 | 上海辉纳思光电科技有限公司 | Phosphonic acid derivative of carbazole, quantum dot light emitting device and perovskite solar cell |
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