CN107793502B - Oxime ester photoinitiator, preparation method thereof, photocuring composition and application thereof - Google Patents
Oxime ester photoinitiator, preparation method thereof, photocuring composition and application thereof Download PDFInfo
- Publication number
- CN107793502B CN107793502B CN201610807375.8A CN201610807375A CN107793502B CN 107793502 B CN107793502 B CN 107793502B CN 201610807375 A CN201610807375 A CN 201610807375A CN 107793502 B CN107793502 B CN 107793502B
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- CN
- China
- Prior art keywords
- photoinitiator
- oxime ester
- structural formula
- cycloalkyl
- ester photoinitiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 Oxime ester Chemical class 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000016 photochemical curing Methods 0.000 title abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 125000004185 ester group Chemical group 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006146 oximation reaction Methods 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000011800 void material Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 125000002541 furyl group Chemical group 0.000 claims description 5
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 125000004799 bromophenyl group Chemical group 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 125000000068 chlorophenyl group Chemical group 0.000 claims description 3
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000006501 nitrophenyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 125000006737 (C6-C20) arylalkyl group Chemical group 0.000 abstract 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 150000001875 compounds Chemical class 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 208000016261 weight loss Diseases 0.000 description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000011345 viscous material Substances 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- 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
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
-
- 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
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
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- 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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
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Abstract
The invention provides an oxime ester photoinitiator, a preparation method thereof, a photocuring composition and application thereof. The oxime ester photoinitiator has a structure shown as a general formula (I):
wherein R is1Is C substituted by cycloalkyl1‑C20Alkyl groups of (a); r2Is C1‑C20Straight-chain or branched alkyl of C3‑C20Cycloalkyl of, C4‑C20Cycloalkylalkyl or alkylcycloalkyl, C6‑C20Aryl or aralkyl radicals or C4‑C20Heterocyclyl group, and R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; ar is a substituent containing an aromatic ring or a heteroaromatic ring; y is C1‑C10And carbon or hydrogen in Y may be optionally substituted with N, O, S, OH, halogen, or an ester group; a is carbonyl or null. Because the 9-site nitrogen in carbazole of the oxime ester photoinitiator forms a ring with the benzene ring in carbazole, the oxime ester photoinitiator has high activity and high heat resistance.
Description
Technical Field
The invention relates to the technical field of organic photocuring, and particularly relates to an oxime ester photoinitiator, a preparation method thereof, a photocuring composition and application thereof.
Background
The photoinitiator is an active intermediate which absorbs radiation energy and generates chemical change through excitation to generate the initiating polymerization capability, and plays an important role in an organic photocuring system, so the development of the photoinitiator is closely inseparable with the development of an ultraviolet curing technology. Oxime ester compounds are well known in the art as photoinitiators, and carbazole oxime ester photoinitiators are widely used due to their good application performance, for example, patents or patent applications with publication numbers CN1922142A, CN1928716A, CN101048337A, CN101528693A, and CN101508744A all disclose different carbazole oxime ester photoinitiators and point out their application in color filters, black matrices, photo spacers, and liquid crystal segmentation and orientation.
However, in practical applications, the chemical properties of the initiator at high temperatures and the mechanical properties of the composition containing the initiator at high temperatures are also important considerations. The initiator needs to have better thermal stability in the exposure and plating processes, otherwise the decomposition at high temperature can affect the initiation efficiency, and the thermal stability of the material formed at the later stage of the composition is a problem to be considered, because the migration of the initiator can cause the deformation or aging of the material. The heat resistance of the existing photoinitiators is difficult to balance, although to some extent they are otherwise more or less satisfactory. Therefore, a balance between the reactivity and heat resistance of the initiator at high temperatures is required, and a photoinitiator which is not easily decomposed at high temperatures and has high activity has been developed.
Disclosure of Invention
The invention mainly aims to provide an oxime ester photoinitiator, a preparation method thereof, a photocuring composition and application thereof, and aims to solve the problem that the photoinitiator in the prior art is difficult to have high activity and high heat resistance at the same time.
To achieve the above object, according to one of the present inventionIn one aspect, an oxime ester photoinitiator is provided, the oxime ester photoinitiator having a structure represented by general formula (I):
wherein R is1Is C substituted by cycloalkyl1-C20Alkyl groups of (a); r2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl group, and R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; ar is a substituent containing an aromatic ring or a heteroaromatic ring; y is C1-C10And carbon or hydrogen in Y may optionally be substituted with N, O, S, OH, halogen, or an ester group; a is carbonyl or empty, the void of which is represented by1The attached C is directly attached to the benzene ring.
Further, the above R1Is C substituted by cycloalkyl1-C10Is preferably C substituted by cycloalkyl2-C6Alkyl groups of (a); preferably R2Is C1-C10Straight chain alkyl group of (1), C1-C10Branched alkyl of C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl of (C)4-C10Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl group, and R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; preferably Ar is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenylsulfide, pyridyl, thienyl, furyl, 2-methyl-thienyl, 3-methylthiophenyl, furyl, 2-methyl-furyl, 3-methylfuryl; preferably Y is C1-C8Straight chain alkyl ofA branched alkyl group.
Further, the structure of the above general formula (I) is:
according to another aspect of the present application, there is provided a method for preparing an oxime ester photoinitiator having a structure represented by general formula (I):
the preparation method comprises the following steps: step S1, carrying out substitution reaction on the raw material a with the structural formula A and the raw material B with the structural formula B to obtain an intermediate C with the structural formula C; step S2, carrying out Friedel-crafts reaction on the intermediate c, the raw material D with the structural formula D and the raw material E with the structural formula E to obtain an intermediate F with the structural formula F; step S3, carrying out oximation reaction on the intermediate f to obtain an intermediate G with a structural formula G; and step S4, carrying out esterification reaction on the intermediate g to obtain the oxime ester photoinitiator, wherein the structural formula A is
Structural formula B is
Structural formula C is
Structural formula D is
Structural formula E is
Structural formula F is
The structural formula G is
Wherein R is1Is C substituted by cycloalkyl1-C20Alkyl groups of (a); r2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl group, and R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; ar is a substituent containing an aromatic ring or a heteroaromatic ring; y is C1-C10And carbon or hydrogen in Y may optionally be substituted with N, O, S, OH, halogen, or an ester group; a is carbonyl or empty, the void of which is represented by1The connected C is directly connected with a benzene ring; x represents halogen; a in the general formula (I) is null, then R1' represents R1In the general formula (I), A is a carbonyl group, then R1' represents R1-CH2-。
Further, the step S1 includes: and (2) carrying out substitution reaction on the raw material a and the raw material b under an alkaline condition and the catalytic action of a phase transfer catalyst to obtain a synthetic intermediate c, wherein the alkaline condition is preferably a condition that the pH value is 7-10, further preferably an alkaline condition is formed by adopting potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide, sodium carbonate and/or ammonia water, and more preferably the phase transfer catalyst is a quaternary ammonium salt.
Furthermore, the substitution reaction is carried out by adopting a scheme of reflux reaction at 80-200 ℃, and the preferred time of the reflux reaction is 12-24 h.
Further, the above step S2 is carried out in an organic solvent under the catalytic action of aluminum trichloride or zinc chloride.
Further, a in the above general formula (I) is empty, and step S3 includes subjecting the intermediate f to oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate to obtain an intermediate g; a in the above general formula (I) is carbonyl, and step S3 includes subjecting intermediate f to oximation reaction with nitrite at room temperature in the presence of an organic solvent and an acid to obtain intermediate g, preferably concentrated hydrochloric acid.
Further, the step S4 includes reacting the intermediate g with (R)2-CO)2O or R2Carrying out esterification reaction on-CO-Cl to obtain oxime ester photoinitiator, wherein R2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl group, and R2The carbon or hydrogen in (A) may optionally be replaced by N, O, S, OH or an ester group.
According to a further aspect of the present invention, there is provided a photocurable composition comprising a photoinitiator, which is any one of the oxime ester photoinitiators described above.
According to a further aspect of the present invention there is provided the use of a photoinitiator in a colour filter, black matrix, optical spacer or liquid crystal division alignment, the photoinitiator being an oxime ester photoinitiator as described above.
By applying the technical scheme of the invention, the 9-site nitrogen in carbazole of the oxime ester photoinitiator forms a ring with the benzene ring in carbazole, so that the photoinitiator has excellent heat resistance and relatively excellent photosensitivity, and further provides the photoinitiator with high activity and high heat resistance for the field.
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, the photoinitiators of the prior art have difficulty in balancing between activity and heat resistance, thus resulting in the lack of photoinitiators in the prior art that combine high activity and high heat resistance. In order to solve the problem, the application provides an oxime ester photoinitiator, a preparation method thereof, a photocuring composition and application thereof.
In one exemplary embodiment of the present application, an oxime ester photoinitiator is provided, the oxime ester photoinitiator having a structure represented by general formula (I):
wherein R is1Is C substituted by cycloalkyl1-C20Alkyl groups of (a); r2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl group, and R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; ar is a substituent containing an aromatic ring or a heteroaromatic ring; y is C1-C10And carbon or hydrogen in Y may optionally be substituted with N, O, S, OH, a halogen, or an ester group (including all chemically acceptable forms of substitution); a is carbonyl or empty, the void of which is represented by1The attached C is directly attached to the benzene ring.
Experiments prove that the 9-site nitrogen in carbazole of the oxime ester photoinitiator forms a ring with a benzene ring in carbazole, so that the photoinitiator has excellent heat resistance and relatively excellent photosensitivity, and further provides the photoinitiator with high activity and high heat resistance for the field.
In order to make the photoinitiator easier to prepare, the method comprisesSo that it is more easily popularized and applied, the above R is preferable1Is C substituted by cycloalkyl1-C10Is preferably C substituted by cycloalkyl2-C6Alkyl groups of (a); preferably said R2Is C1-C10Straight chain alkyl group of (1), C1-C10Branched alkyl of C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl of (C)4-C10Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl, and said R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; preferably, Ar is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenylsulfide, pyridyl, thienyl, furyl, 2-methyl-thienyl, 3-methylthiophenyl, furyl, 2-methyl-furyl, 3-methylfuryl; preferably, Y is C1-C8Linear or branched alkyl groups of (a).
In some specific embodiments herein, it is preferred that the structure of formula (I) above is:
the photoinitiator represented by the structural formulas is more stable in structure and relatively easy to synthesize.
The oxime ester photoinitiator shown in the general formula (I) can also be prepared by R1、R2Or Y are polymerized in conjunction with each other to form a dimer, and these dimerization products are considered to exhibit application properties similar to those of the compound represented by the general formula (I).
In another exemplary embodiment of the present application, a method for preparing an oxime ester photoinitiator is provided, the oxime ester photoinitiator having a structure represented by general formula (I):
the preparation method comprises the following steps: step S1, carrying out substitution reaction on the raw material a with the structural formula A and the raw material B with the structural formula B to obtain an intermediate C with the structural formula C; step S2, carrying out Friedel-crafts reaction on the intermediate c, the raw material D with the structural formula D and the raw material E with the structural formula E to obtain an intermediate F with the structural formula F; step S3, carrying out oximation reaction on the intermediate f to obtain an intermediate G with a structural formula G; and step S4, carrying out esterification reaction on the intermediate g to obtain the oxime ester photoinitiator, wherein the structural formula A is
Structural formula B is
Wherein X represents halogen; structural formula C is
Structural formula D is
Structural formula E is
Wherein, if A in the general formula (I) is null, R is1' represents R1In the general formula (I), A is a carbonyl group, then R1' represents R1-CH 2-; structural formula F is
The structural formula G is
Wherein R is1Is C substituted by cycloalkyl1-C20Alkyl groups of (a); r2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl group, and R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; ar is a substituent containing an aromatic ring or a heteroaromatic ring; y is C1-C10And carbon or hydrogen in Y may optionally be substituted with N, O, S, OH, halogen, or an ester group; a is carbonyl or empty, the void of which is represented by1The attached C is directly attached to the benzene ring.
The key of the preparation method is that in step S1, after the parent chain of the photoinitiator is determined by using step S1, steps S2 to S4 are adjusted on the basis of the conventional Friedel-crafts reaction, oximation reaction and esterification reaction.
In a preferred embodiment of the present application, the step S1 includes: and (2) carrying out substitution reaction on the raw material a and the raw material b under an alkaline condition and the catalytic action of a phase transfer catalyst to obtain a synthetic intermediate c, wherein the alkaline condition is preferably a condition that the pH value is 7-10, further preferably an alkaline condition is formed by adopting potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide, sodium carbonate and/or ammonia water, and more preferably the phase transfer catalyst is a quaternary ammonium salt. The reaction rate can be increased by carrying out the above reaction under alkaline conditions and in the presence of a phase transfer catalyst.
Further, in order to increase the conversion rate of the raw material, the substitution reaction is preferably performed by a reflux reaction at 80 to 200 ℃, and the reflux reaction time is more preferably 12 to 24 hours. The temperature of the reflux reaction may be appropriately adjusted according to the boiling points of the solvent and the raw material b selected for the reflux reaction.
The above steps S2 to S4 can be performed by referring to the prior art and adjusting the test conditions, for example, by referring to the methods disclosed in the patent applications 200910030326.8, 201410334871.7, 201510645356.5, 201610449965.8.
In order to further improve the reaction efficiency and the product yield, it is preferable that the above step S2 is carried out in an organic solvent under the catalytic action of aluminum trichloride or zinc chloride. Wherein the organic solvent can be dichloromethane, dichloroethane, toluene or benzene.
Preferably, when a in the general formula (I) is empty, the step S3 includes subjecting the intermediate f to oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate to obtain an intermediate g; and when a in the general formula (I) is carbonyl, step S3 includes subjecting intermediate f to oximation reaction with nitrite or nitrite in the presence of an organic solvent and an acid at room temperature to obtain intermediate g, preferably the acid is concentrated hydrochloric acid.
It is further preferable that the step S4 includes reacting the intermediate g with (R)2-CO)2O or R2Carrying out esterification reaction on-CO-Cl to obtain oxime ester photoinitiator, wherein R2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl group, and R2The carbon or hydrogen in (A) may optionally be replaced by N, O, S, OH or an ester group.
In yet another exemplary embodiment of the present application, a photocurable composition is provided that includes a photoinitiator that is an oxime ester photoinitiator according to the present application.
Since the oxime ester photoinitiator has both high activity and high heat resistance, a photocurable material formed from a photocurable composition containing the oxime ester photoinitiator has high stability and improved curing efficiency.
Without limitation, the photoinitiator can be used in Photo-curing compositions for producing color Resists (RGB), black resists (BM), steric barriers (Photo-spacers), dry films, semiconductor photoresists, inks, and the like. Application practices show that compared with the existing similar photoinitiators, the oxime ester photoinitiator has low cost and very good heat resistance, and the photosensitive property in the photocuring composition is not influenced.
Furthermore, the invention also comprises the application of the oxime ester photoinitiator in the field of photocuring, and the oxime ester photoinitiator or the mixture thereof can be directly used in a formula and can also be matched with other photoinitiators for use.
Further, the application also provides an application of the photoinitiator in color filters, black matrixes, optical spacers or liquid crystal segmentation and orientation, wherein the photoinitiator is the oxime ester photoinitiator.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.
Preparation examples
Example 1:
(1) preparation of intermediate 1a
Adding 125g of raw material a, 3g of tetrapropylammonium bromide and 300mL of 1, 2-dibromoethane into a 1000mL four-neck flask to form a first reaction system, heating and refluxing the first reaction system at 85 ℃, slowly dropwise adding 150g of 40% NaOH solution into the first reaction system for about 1h, heating, refluxing and stirring overnight after dropwise adding, slowly pouring the materials into 900g of deionized water containing 2% HCl, separating an organic layer, pouring the organic layer into 300mL of 1% sodium bicarbonate aqueous solution, washing a dichloroethane layer with water to be neutral, removing dichloroethane by rotary evaporation to obtain a pale yellow viscous liquid, recrystallizing methanol to obtain a white solid, drying in an oven at 100 ℃ for 2h to obtain 93g of an intermediate 1a,1H-NMR(CDCl3，500MHz)：3.0311-3.0592(2H,t)，4.1789-4.1802(2H，t)，6.9571-7.3757(7H，m)，MS(m/z):194(M+1)+。
(2) preparation of intermediate 1b
77.3g of the raw material 1a, 107g of aluminum trichloride and 200mL of methylene chloride were placed in a 1000mL four-necked flask to prepare a first mixed system, and the temperature of the first mixed system was lowered to 0 ℃ by means of an ice water bath. Dissolving 62g of raw material 1c in 50mL of dichloromethane, then loading the mixture into a dropping funnel, controlling the temperature below 10 ℃, dropwise adding the mixed solution of 1c and dichloromethane into a first mixed system, completing dropwise adding for about 2 hours to form a second reaction system, continuing stirring the second reaction system for 24 hours after dropwise adding, continuing controlling the temperature, dropwise adding 59g of mixed solution of 1d and 50mL of dichloromethane to form a third reaction system, tracking the liquid phase until the raw material does not change, then slowly pouring the material into 200g of deionized water containing 2% of sodium bicarbonate, stirring, separating a dichloromethane layer, then carrying out column chromatography purification on the dichloromethane layer, carrying out rotary evaporation on the purified product to obtain a light yellow solid, drying in an oven at 100 ℃ for 2 hours to obtain 84.3g of intermediate 1b, wherein the purity is 98%.
MS(m/z):422(M+1)+。
(3) Preparation of intermediate 1c
Adding 84g of the intermediate 1b, 20g of 37% hydrochloric acid, 23g of isoamylnitrite and 100mL of tetrahydrofuran into a 500mL four-neck flask to form a fourth reaction system, stirring the fourth reaction system for 5 hours at the temperature of 20-30 ℃, and stopping reaction; the material was poured into a 2000mL beaker, 1000mL of water was added, stirring was carried out, 200mL of methylene chloride was used for extraction, and 50g of anhydrous MgSO was added to the extract4Drying, and adding MgSO 24Filtering the extractive solution, evaporating the filtrate under reduced pressure to remove solvent, rotating the bottle to obtain oily viscous substance, and pouring the viscous substance into 150mL stoneStirring in oil ether, filtering to obtain white powdery solid, oven drying at 80 deg.C for 5 hr to obtain intermediate 1b67g with purity of 98%, MS (M/z):451(M +1)+。
(4) Preparation of Compound 1
Adding 45g of intermediate 1c and 100mL of dichloromethane into a 250mL four-neck flask, stirring at room temperature for 5min, then dropwise adding 10g of propionyl chloride into the four-neck flask, forming a fifth reaction system after dropwise adding for about 30min, continuously stirring the fifth reaction system for 2h, and then adding 5% NaHCO into the four-neck flask3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 200mL water for 2 times, 50g anhydrous MgSO4Drying, and adding MgSO 24Filtering the extract, evaporating the solvent after filtering to obtain viscous liquid, recrystallizing with methanol to obtain white solid powder, and filtering to obtain 48g of product with purity of 99%.
The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：1.0833-1.0954(3H,t)，1.4998-1.5102(5H，m)，1.6243-1.6999(4H，m)，2.2218-2.7511(3H，m)，2.3527(1H,s)，3.0312-3.0367(2H,t)，4.1706-4.1893(2H，t)，7.1751-7.8777(10H，m)。
MS(m/z):507(M+1)+。
Example 2
(1) Preparation of intermediate 2a
125g of raw material a, 4g of tetrabutylammonium bromide and 2b300mL as raw materials are added into a 1000mL four-neck flask to form a first reaction system, the first reaction system is heated and refluxed at 85 ℃, 200g of 40% KOH solution is slowly added dropwise into the first reaction system for about 1h, the mixture is heated, refluxed and stirred overnight after the dropwise addition is finished, and then the materials are mixedSlowly pouring into 900g of deionized water containing 2% HCl, separating an organic layer, then pouring the organic layer into 300mL of 1% sodium bicarbonate aqueous solution, washing a dichloroethane layer with water to be neutral, removing the dichloroethane by rotary evaporation to obtain a light yellow viscous liquid, recrystallizing methanol to obtain a white solid, drying in an oven at 100 ℃ for 2 hours to obtain 105g of an intermediate 2a,1H-NMR(CDCl3，500MHz)：2.0991-3.1253(2H,m)，2.5371-2.5502(2H,t)，3.8474-3.862(2H，t)，6.9478-7.3996(7H，m)，MS(m/z):207(M+1)+。
(2) preparation of intermediate 2b
A1000 mL four-necked flask was charged with 83g of the starting material 2a, 107g of aluminum trichloride, and 200mL of methylene chloride to prepare a first mixed system, and the temperature of the first mixed system was lowered to 0 ℃ by means of an ice-water bath. Dissolving 59g of raw material 2c in 50mL of dichloromethane, then loading the mixture into a dropping funnel, controlling the temperature below 10 ℃, dropwise adding the mixed solution of the 2c and the dichloromethane into the first mixed system, forming a second reaction system after about 2h of dropwise adding, continuously stirring the second reaction system for 24h after dropwise adding, continuously controlling the temperature, dropwise adding the mixed solution of 59g of 2d and 50mL of dichloromethane to form a third reaction system, tracking the liquid phase until the raw material does not change any more, then slowly pouring the materials into 200g of deionized water containing 2% of sodium bicarbonate, stirring, separating a dichloromethane layer, then carrying out column chromatography purification on the dichloromethane layer, carrying out rotary evaporation on the purified product to obtain a light yellow solid, drying in an oven at 100 ℃ for 2h to obtain 94g of an intermediate 2b with the purity of 98%, MS (M/z):428(M +1)+。
(3) Preparation of intermediate 2c
Adding 86g of intermediate 2b, 28g of hydroxylamine hydrochloride, 32g of sodium acetate, 150mL of ethanol and 50mL of water into a 500mL four-neck flask to form a fourth reaction system, heating at 85 ℃, refluxing and stirring the fourth reaction system for 5 hours, stopping the reaction, and adding the mixtureThe mixture was poured into a 2000mL beaker, 1000mL of water was added thereto, the mixture was stirred, 200mL of methylene chloride was used for extraction, and 50g of anhydrous MgSO was added to the extract4Drying, and adding MgSO 24Filtering the extractive solution, rotary evaporating the filtrate under reduced pressure to remove solvent, rotating the bottle to obtain oily viscous substance, pouring the viscous substance into 150mL petroleum ether, stirring, filtering to obtain white powdery solid, oven drying at 60 deg.C for 5 hr to obtain intermediate 2c63g, purity 98%, MS (M/z):423(M +1)+。
(4) Preparation of Compound 2
Adding 42g of intermediate 2c and 100mL of dichloromethane into a 250mL four-neck flask, stirring at room temperature for 5min, then dropwise adding 13g of propionic anhydride into the four-neck flask, forming a fifth reaction system after dropwise adding for about 30min, continuously stirring the fifth reaction system for 2h, and then adding 5% NaHCO into the four-neck flask3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 200mL water for 2 times, 50g anhydrous MgSO4Drying, and adding MgSO 24Filtering the extract, evaporating the solvent after filtering to obtain viscous liquid, recrystallizing with methanol to obtain white solid powder, and filtering to obtain 48g of product with purity of 99%.
The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：0.9881-1.0109(3H,t)，1.4401-1.4497(7H，m)，1.6247-1.6285(4H，m)，2.0842-2.31099(2H，m)，2.2607-2.2731(2H,m),2.4776-2.5003(2H,t)，3.7926-3.8139(2H，t)，7.1748-8.0050(8H，m)。
MS(m/z):499(M+1)+。
Examples 3 to 16:
compounds 3 to 16 shown in table 1 below were synthesized using the corresponding starting materials with reference to the methods of example 1 and/or 2.
The structure of the target product and its mass spectral data are listed in table 1:
TABLE 1
Evaluation of Performance
1. Evaluation of thermal stability of photoinitiator
The thermal decomposition temperature of the compound is an important parameter for measuring the thermal stability of the compound, and thermogravimetric analysis is carried out on the photoinitiator and the comparative compound by utilizing a thermal weight loss analyzer (PE STA 6000). The temperature of a portion where a tangent line of the initial non-weight-reduction or gradual-weight-reduction portion and a tangent line of the inflection point where the weight is rapidly reduced intersect is set as the thermal decomposition temperature T (° c), and the evaluation is performed according to the following criteria.
The thermal decomposition temperature T (DEG C) is more than 230, and the thermal stability is recorded as ^ excellent;
the thermal decomposition temperature T (DEG C) is between 200 and 230, and the thermal stability is marked as O;
the thermal stability was recorded as ●, with a thermal decomposition temperature T (. degree.C.) of 200 or less.
TABLE 2 thermal stability analysis
The structures of OXE-1 (see patent application publication No. CN 1241562A), OXE-2 (see patent application publication No. CN 1514845A), TR-PBG-304 (see patent application publication No. CN 101508744A), and Compound X (see patent application publication No. CN 103130919A) in Table 2 are as follows:
from the above table, it can be seen that the thermal weight loss temperature of the oxime ester photoinitiator is higher than that of the existing oxime ester photoinitiator, and the thermal stability of the initiator is obviously improved after the 9-position nitrogen in carbazole and the benzene ring in carbazole are cyclized, especially from the comparison of compound 4 and TR-PBG-304 and the comparison of compound 10 and compound X, which further shows that the cyclization brings the effect which cannot be expected by a person skilled in the art for improving the thermal resistance.
2. Film Forming Property test
The film-forming properties of the photoinitiators of formula (I) according to the invention and of the oxime ester initiators in general were evaluated by formulating exemplary photocurable compositions.
(1) A photocurable composition was prepared as follows
In the above composition, the photoinitiator is a compound represented by formula (I) disclosed in the present invention or a photoinitiator known in the prior art (for comparison).
(2) Film forming property
Stirring the light-cured composition under a yellow light, taking the composition out of a PET template, rolling and coating the composition to form a film, (drying the dissolved composition at 90 ℃ for 5min to remove the solvent) A coating film having a thickness of about 2 μm was formed. Cooling the substrate with the coating film to room temperature, attaching a mask plate, and irradiating with a high-pressure mercury lamp (model RW-UV70201 exposure machine, light intensity 50 mW/cm)2) The coating was exposed to light for 30 seconds. Visually observed to evaluate the film formation in the exposed area.
Then soaking in 1% NaOH water solution at 25 deg.C for 30s for development, washing with ultrapure water, and air drying; and then post-baking for 30min in an oven at 240 ℃ to obtain the pattern transferred by the mask plate. The pattern on the substrate was observed with a Scanning Electron Microscope (SEM) to evaluate developability, pattern integrity, and heat resistance of the formed film.
The evaluation criteria for film formation were as follows:
very good: the surface of the film is smooth;
o: the film surface has flaws;
●: the film formation was impossible.
The evaluation criteria for developability were as follows:
very good: no residue was observed in the unexposed parts;
o: a small amount of residue was observed in the unexposed parts, but the residual amount was acceptable;
●: a clear residue was observed in the unexposed parts.
The evaluation criteria for pattern integrity were as follows:
very good: no pattern defects were observed;
o: a small part of the pattern was observed to have some defects;
●: many pattern defects were clearly observed.
Evaluation of film formation Heat resistance:
the cured film was subjected to thermogravimetric analysis using a thermogravimetric analyzer (PE STA 6000). The temperature of a portion where a tangent line of the initial non-weight-reduction or gradual-weight-reduction portion and a tangent line of the inflection point where the weight is rapidly reduced intersect is set as the thermal decomposition temperature T (° c), and the evaluation is performed according to the following criteria.
The thermal decomposition temperature T (DEG C) is 230 or more, and the heat resistance is recorded as ^ excellent;
the thermal decomposition temperature T (DEG C) is between 200 and 230, and the heat resistance is marked as O;
the thermal decomposition temperature T (. degree. C.) was 200 or less, and the heat resistance was recorded as ●.
The evaluation results are summarized in table 3.
TABLE 3
| Composition comprising a metal oxide and a metal oxide | Photoinitiator | Film formation conditions | Developability | Integrity of pattern | Heat resistance |
| Composition 1 | Compound 1 | ◎ | ◎ | ◎ | ◎ |
| Composition 2 | Compound 2 | ◎ | ◎ | ◎ | ◎ |
| Composition 3 | Compound 4 | ◎ | ◎ | ◎ | ◎ |
| Composition 4 | Compound 5 | ◎ | ◎ | ◎ | ◎ |
| Composition 5 | Compound 6 | ◎ | ◎ | ◎ | ◎ |
| Composition 6 | Compound 8 | ◎ | ◎ | ◎ | ◎ |
| Composition 7 | Compound 10 | ◎ | ◎ | ◎ | ◎ |
| Composition 8 | Compound 12 | ◎ | ◎ | ◎ | ◎ |
| Composition 9 | Compound 14 | ◎ | ◎ | ◎ | ◎ |
| Composition 10 | Compound 16 | ◎ | ◎ | ◎ | ◎ |
| Composition 11 | OXE-1 | ○ | ○ | ○ | ● |
| Composition 12 | OXE-2 | ◎ | ◎ | ◎ | ○ |
| Composition 13 | TR-PBG-304 | ◎ | ◎ | ◎ | ○ |
| Composition 14 | Compound X | ◎ | ◎ | ◎ | ● |
As can be seen from Table 3, compared with the prior oxime ester photoinitiator, the photocuring composition containing the photoinitiator of the invention has basically equivalent film forming property, developability and pattern integrity, and the heat resistance is obviously higher than that of a comparison compound, while the prior oxime ester photoinitiator shows obvious defects. Particularly, as can be seen from the comparison between the composition 3 and the composition 13 and the comparison between the composition 7 and the composition 14, after the 9-position nitrogen in carbazole is cyclized with the benzene ring in carbazole, the composition retains good film-forming property, developability and pattern integrity, but the heat resistance of the composition is obviously improved, and further, the cyclization brings unexpected effects to the improvement of the heat resistance for the people skilled in the art on the basis of keeping the original high activity of the initiator
On the whole, the photoinitiator shown in the formula (I) disclosed by the invention has the advantages of excellent application performance, strong heat resistance and good application prospect.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
experiments prove that the 9-site nitrogen in carbazole of the oxime ester photoinitiator forms a ring with a benzene ring in carbazole, so that the photoinitiator has excellent heat resistance and relatively excellent photosensitivity, and further provides the photoinitiator with high activity and high heat resistance for the field.
Since the oxime ester photoinitiator has both high activity and high heat resistance, a photocurable material formed from a photocurable composition containing the oxime ester photoinitiator has high stability and improved curing efficiency.
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 (20)
1. An oxime ester photoinitiator is characterized by having a structure shown as a general formula (I):
wherein,
R1is C substituted by cycloalkyl1-C20Alkyl groups of (a);
R2is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl, and said R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group;
ar is a substituent containing an aromatic ring or a heteroaromatic ring;
y is C1-C10And carbon or hydrogen in Y may optionally be substituted with N, O, S, OH, halogen, or an ester group;
a is carbonyl or empty, the void of which is represented by the formula1The connected C is directly connected with a benzene ring,
or the oxime ester photoinitiator has the following structural formula:
2. the oxime ester photoinitiator as claimed in claim 1, wherein R is R1Is C substituted by cycloalkyl1-C10Alkyl group of (1).
3. The oxime ester photoinitiator as claimed in claim 2 wherein R is1Is C substituted by cycloalkyl2-C6Alkyl group of (1).
4. The oxime ester photoinitiator as claimed in claim 2 wherein R is2Is C1-C10Straight chain alkyl group of (1), C1-C10Branched alkyl of C3-C10Cycloalkyl of, C4-C10Cycloalkylalkyl of (C)4-C10Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl, and said R2The carbon or hydrogen in (A) may optionally be replaced by N, O, S, OH or an ester group.
5. An oxime ester photoinitiator as claimed in claim 2 wherein Ar is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenylsulfide, pyridyl, thienyl, furyl, 2-methyl-thienyl, 3-methylthiophenyl, 2-methyl-furyl, 3-methylfuryl.
6. The oxime ester photoinitiator as claimed in claim 2, wherein Y is C1-C8Linear or branched alkyl groups of (a).
7. The oxime ester photoinitiator as claimed in claim 1, wherein the structure of the general formula (I) is:
8. the preparation method of the oxime ester photoinitiator is characterized in that the oxime ester photoinitiator has a structure shown as a general formula (I):
the preparation method comprises the following steps:
step S1, carrying out substitution reaction on the raw material a with the structural formula A and the raw material B with the structural formula B to obtain an intermediate C with the structural formula C;
step S2, carrying out Friedel-crafts reaction on the intermediate c, the raw material D with the structural formula D and the raw material E with the structural formula E to obtain an intermediate F with the structural formula F;
step S3, carrying out oximation reaction on the intermediate f to obtain an intermediate G with a structural formula G; and
step S4, the intermediate g is subjected to esterification reaction to obtain the oxime ester photoinitiator, wherein,
the structural formula A is
The structural formula B is
The structural formula C is
The structural formula D is
The structural formula E is
The structural formula F is
The structural formula G is
Wherein,
R1is C substituted by cycloalkyl1-C20Alkyl groups of (a); r2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl, and said R2The carbon or hydrogen in (A) can be optionally substituted by N, O, S, OH or an ester group; ar is a substituent containing an aromatic ring or a heteroaromatic ring; y is C1-C10And carbon or hydrogen in Y may optionally be substituted with N, O, S, OH, halogen, or an ester group; a is carbonyl or empty, the void of which is represented by the formula1The connected C is directly connected with a benzene ring; x represents halogen; a in the general formula (I) is null, then R1' represents R1In the general formula (I), A is a carbonyl group, then R1' represents R1-CH2-。
9. The method for preparing a composite material according to claim 8, wherein the step S1 includes:
and (3) carrying out substitution reaction on the raw material a and the raw material b under the alkaline condition and the catalytic action of a phase transfer catalyst to obtain the intermediate c.
10. The method according to claim 9, wherein the alkaline condition is a condition of pH 7 to 10.
11. The method of claim 10, wherein the alkaline condition is formed using potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide, sodium carbonate, and/or ammonia water.
12. The method according to claim 11, wherein the phase transfer catalyst is a quaternary ammonium salt.
13. The preparation method according to claim 9, wherein the substitution reaction is performed by a reflux reaction at 80-200 ℃.
14. The preparation method according to claim 13, wherein the time of the reflux reaction is 12-24 hours.
15. The method according to claim 8, wherein the step S2 is carried out in an organic solvent under the catalysis of aluminum trichloride or zinc chloride.
16. The method according to claim 8,
a in the general formula (I) is empty, and the step S3 comprises the step of carrying out oximation reaction on the intermediate f under the action of hydroxylamine hydrochloride and sodium acetate to obtain the intermediate g;
a in the general formula (I) is carbonyl, and the step S3 comprises the oximation reaction of the intermediate f and nitrite at room temperature in the presence of an organic solvent and an acid to obtain the intermediate g.
17. The method of claim 16, wherein the acid is concentrated hydrochloric acid.
18. The method according to claim 8, wherein step S4 includes reacting intermediate g with (R)2-CO)2O or R2Carrying out the esterification reaction by-CO-Cl to obtain the oxime ester photoinitiator, wherein R2Is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl of C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl radical, C6-C20Aralkyl or C4-C20Heterocyclyl, and said R2The carbon or hydrogen in (A) may optionally be replaced by N, O, S, OH or an ester group.
19. A photocurable composition comprising a photoinitiator, characterised in that the photoinitiator is an oxime ester photoinitiator according to any one of claims 1 to 7.
20. Use of a photoinitiator in a color filter, black matrix, photo spacer or liquid crystal division alignment, wherein the photoinitiator is an oxime ester photoinitiator according to any one of claims 1 to 7.
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