CN109957046A - Fluorine-containing fluorenes oxime ester lightlike initiating agent, the Photocurable composition comprising it and its application - Google Patents
Fluorine-containing fluorenes oxime ester lightlike initiating agent, the Photocurable composition comprising it and its application Download PDFInfo
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- CN109957046A CN109957046A CN201711415551.4A CN201711415551A CN109957046A CN 109957046 A CN109957046 A CN 109957046A CN 201711415551 A CN201711415551 A CN 201711415551A CN 109957046 A CN109957046 A CN 109957046A
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- China
- Prior art keywords
- fluorine
- alkyl
- oxime ester
- initiating agent
- containing fluorenes
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- 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.)
- Granted
Links
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 45
- -1 fluorenes oxime ester Chemical class 0.000 title claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- 239000011737 fluorine Substances 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 22
- 238000001035 drying Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 11
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 10
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000009161 Espostoa lanata Nutrition 0.000 description 7
- 240000001624 Espostoa lanata Species 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method 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
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 206010067482 No adverse event Diseases 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006146 oximation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 2
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010019133 Hangover Diseases 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 238000001556 precipitation 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
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
- C07C255/64—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of fluorine-containing fluorenes oxime ester lightlike initiating agent, the Photocurable composition comprising it and its applications.The photoinitiator has structure shown in logical formula (I).In fluorine-containing fluorenes oxime ester lightlike initiating agent provided by the present application, by the way that in 9 fluorene structured introducing polymerizable groups, this enables the photoinitiator to be formed to polymerize with substrate so that the photoinitiator have the advantages that it is not easy to migrate.Simultaneously because introducing fluoro-containing group, photoinitiator provided by the present application also has the advantages that efficiency of initiation is high.In addition, the particularity in structure, which makes the photoinitiator also, has the advantages that surface drying performance is good, surface cure effect is good etc..On this basis, above-mentioned photoinitiator has the advantages that not easy to migrate, efficiency of initiation is high, surface drying performance is good and surface cure effect is good etc., and has broad application prospects.
Description
Technical field
The present invention relates to organic synthesis field, in particular to a kind of fluorine-containing fluorenes oxime ester lightlike initiating agent, comprising its
Photocurable composition and its application.
Background technique
The more traditional iconoscope monitor of liquid crystal display device has the advantages that low energy consumption, small in size and radiationless, still
The bad defect of too small, image hangover that there are still visual corners, brightness and contrast.In recent years, with living standards of the people
Continuous improvement, higher requirements are also raised to liquid crystal display device by people, large scale, Gao Huidu, high contrast and wide
Visual angle etc. demands be mentioned, this just to liquid crystal display production used in material more stringent requirements are proposed.
Colored, black photoresist and light separation material are the important component for forming liquid crystal flat panel display, even more advanced lines
Large scale is realized in FPD and the essential material of high-resolution, the oxime ester initiator of high sensitivity are that photoresist and separation material are matched
The important component of side, in recent years, the research in relation to high sensitivity initiator is very burning hot, but these disclosed photoinitiators
Surface drying performance difference and problem easy to migrate still do not solved effectively, this affects the application of material in varying degrees
Energy.
Summary of the invention
The main purpose of the present invention is to provide a kind of fluorine-containing fluorenes oxime ester lightlike initiating agent, include its Photocurable composition
And its application, to solve the problems, such as existing oxime ester lightlike initiating agent surface drying difference and easy to migrate.
To achieve the goals above, the present invention provides a kind of fluorine-containing fluorenes oxime ester lightlike initiating agent, photoinitiator has logical
Structure shown in formula (I):
Wherein, n indicates 1~4 integer；M indicates 1~4 integer；
N R1Separately it is selected from-G- (M ')q, hydrogen, nitro, halogen orM,
Indicate 1~4 integer；Wherein, G is selected from hetero atom or carbonyl, and hetero atom O, N or S, M ' is selected from C1~C20Linear chain or branched chain
Alkyl, C3~C8Naphthenic base, C3~C8Naphthenic base replace C1~C10Alkyl, C6~C20Aryl, C1~C10Alkane
The C that base, nitro replace6~C20The C that aryl, cyano replace6~C20Aryl, C4~C20Heteroaryl, nitro replace C6~C20
The C that heteroaryl or cyano replace6~C20One or more carbon atoms in heteroaryl or M ' are exchanged for heteroatoms, q be 1 or
2；
R2And R2' separately it is selected from polymerizable groups；
Z and Z ' separately indicates empty or carbonyl；
M R3And m ' R5Separately selected from fluorine, by one or more fluorine-substituted linear or branched alkyl groups, by one
Or multiple fluorine-substituted straight or branched alkoxyls；
R4And R6Separately it is selected from C1~C20Linear or branched alkyl group, C3~C20Naphthenic base, C3~C8Naphthenic base
Substituted C1~C10Alkyl, C1~C10Alkyl-substituted C3~C8Naphthenic base, C6~C20Aryl, C4~C20Heteroaryl or
C2~C20Alkenyl.
It applies the technical scheme of the present invention, in fluorine-containing fluorenes oxime ester lightlike initiating agent provided by the present application, by fluorene structured
9 introducing polymerizable groups, this enables the photoinitiator to be formed to polymerize with substrate, so that the photoinitiator
Have the advantages that not easy to migrate.Simultaneously because introducing fluoro-containing group, photoinitiator provided by the present application also has efficiency of initiation
High advantage.In addition, the particularity in structure, which makes the photoinitiator also, has that surface drying performance is good, surface cure effect is good etc.
Advantage.On this basis, above-mentioned photoinitiator is with not easy to migrate, efficiency of initiation is high, surface drying performance is good and surface cure effect
Well equal advantage, and have broad application prospects.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As described in background technique, there is surface drying difference and easy to migrate in existing oxime ester lightlike initiating agent.
In order to solve the above-mentioned technical problems, the present invention provides a kind of fluorine-containing fluorenes oxime ester lightlike initiating agent, which has general formula
(I) structure shown in:
Wherein, n indicates 1~4 integer；M indicates 1~4 integer；
N R1Separately it is selected from-G- (M ')q, hydrogen, nitro, halogen orm’
Indicate 1~4 integer；Wherein, G includes but is not limited to hetero atom or carbonyl, and hetero atom O, N or S, M ' includes but is not limited to C1
~C20Linear or branched alkyl group, C3~C8Naphthenic base, C3~C8Naphthenic base replace C1~C10Alkyl, C6~C20's
Aryl, C1~C10The C that alkyl, nitro replace6~C20The C that aryl, cyano replace6~C20Aryl, C4~C20Heteroaryl, nitro
Substituted C6~C20The C that heteroaryl or cyano replace6~C20One or more carbon atoms in heteroaryl or M ' are by hetero atom
Replace, q is 1 or 2；
R2And R2' separately it is selected from polymerizable groups；Z and Z ' separately indicates empty or carbonyl；M R3And m '
A R5Separately selected from fluorine, by one or more fluorine-substituted linear or branched alkyl groups, by one or more fluorine-substituted
Straight or branched alkoxyl；R4And R6Separately it is selected from C1~C20Linear or branched alkyl group, C3~C20Naphthenic base, C3
~C8The C that naphthenic base replaces1~C10Alkyl, C1~C10Alkyl-substituted C3~C8Naphthenic base, C6~C20Aryl, C4~C20
Heteroaryl or C2~C20Alkenyl.
In fluorine-containing fluorenes oxime ester lightlike initiating agent provided by the present application, by 9 fluorene structured introducing polymerizable groups, this
Enable formed photoinitiator polymerize with substrate so that the photoinitiator have the advantages that it is not easy to migrate.Together
When due to introducing fluoro-containing group, photoinitiator provided by the present application also has the advantages that efficiency of initiation is high.In addition, in structure
Particularity, which makes the photoinitiator also, has the advantages that surface drying performance is good, surface cure effect is good etc..On this basis, above-mentioned light
Initiator has the advantages that not easy to migrate, efficiency of initiation is high, surface drying performance is good and surface cure effect is good etc., and has wide
Application prospect.
In order to further increase the structural stability of above-mentioned fluorine-containing fluorenes oxime ester lightlike initiating agent, it is preferable that M ' includes but not
It is limited to C1~C10Linear or branched alkyl group, C3~C6Naphthenic base, C3~C6Naphthenic base replace C1~C5Alkyl, C6~
C10Aryl, C1~C5The C that alkyl, nitro replace6~C10The C that aryl, cyano replace6~C10Aryl, C4~C10Heteroaryl,
The C that nitro replaces6~C10The C that heteroaryl or cyano replace6~C10Heteroaryl.
In order to further decrease the migration of above-mentioned fluorine-containing fluorenes oxime ester lightlike initiating agent, it is preferable that R2And R2' independently
Ground is selected from the polymerizable groups containing double bond or epoxy group.
In a kind of preferred embodiment, R2And R2' separately it is selected from C2~C12Alkenyl or R2And R2' in
One or more-CH2Can each independently by-O-,It is replaced；
Preferably, R2And R2' separately it is selected from C3~C8Alkenyl or R2Middle one or more-CH2It can be each
From independently by-O-,It is replaced.
In a kind of preferred embodiment, R2And R2' separately it is selected from the C that Oxyranyle replaces1~C10Alkyl or
The C that propylene oxide base replaces1~C10Alkyl or R2And R2' in C1~C10One or more of alkyl-CH2Each independently
Quilt-O-,Or-O-CH2-CH(OH)-CH2- O- replaces.
In a kind of preferred embodiment, R2And R2' it is separately END CAPPED GROUP selected from Oxyranyle or cyclopropyl alkyl
The C of group1~C8Alkyl, alternatively, R2And R2' in C1~C8One or more of alkyl-CH2Each independently by-O-, Or-O-CH2-CH(OH)-CH2Replaced-O- or in Oxyranyle or propylene oxide base
H can be by C1~C4Alkyl replaced.
Preferably, m R3And a R of m '5Separately selected from F, In selection
Group is stated as R3And R5Be conducive to further increase the efficiency of initiation of photoinitiator.
Preferably, R4And R6Separately it is selected from C1~C6Linear or branched alkyl group, C3~C10Naphthenic base, C3~C6
The C that naphthenic base replaces1~C8Alkyl, C1~C8Alkyl-substituted C3~C6Naphthenic base or C6~C12Aryl.
It is highly preferred that R4And R6Separately it is selected from phenyl, C1~C4Linear or branched alkyl group, C3~C8Naphthenic base
Or C3~C6The C that naphthenic base replaces1~C4Alkyl.
It is highly preferred that fluorine-containing fluorenes oxime ester lightlike initiating agent is selected from
One of group of composition is a variety of.
According to another aspect of the present invention, the present invention also provides fluorine-containing fluorenes oxime esters light shown in above-mentioned logical formula (I) to draw
Send out the preparation method of agent, including the following steps:
(1) preparation of intermediate a
Under the catalytic action of alchlor or zinc chloride, friedel-crafts acylation occurs in organic solvent for raw material a and raw material b
Reaction, obtains intermediate a；Synthetic route is as follows:
A is empty or methylene.
(2) preparation of intermediate b
When intermediate a carries out oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate, A is sky, generates intermediate b,
Synthetic route is as follows:
In the presence of concentrated hydrochloric acid, when intermediate a and nitrous acid ester or nitrite carry out oximation reaction under room temperature, A
For methylene, intermediate b is generated, synthetic route is as follows:
(3) preparation of product
Intermediate b and acid anhydridesOr chloride compoundsEsterification is carried out, target production is obtained
Object, synthetic route are as follows:
, Z is empty or carbon-based.
Raw materials used in above-mentioned synthesis is known compound, can be commercially available or convenient by known synthetic method
Ground is made, wherein raw material a can according to Chinese Patent Application No. be 201710274018.4 disclosed in synthetic method and obtain.It should
Synthesis process successively includes friedel-crafts acylation, oximation reaction and esterification, these are organic chemical synthesis field
Popular response type.After apparent reaction process, specific reaction condition is to be easy determination to those skilled in the art.
Reaction temperature in step (1) is usually -10~30 DEG C.To the organic solvent type used, there is no especially limits
It is fixed, as long as raw material can be dissolved and had no adverse effects to reaction, preferably methylene chloride, dichloroethanes, benzene, toluene and two
One of group of toluene composition is a variety of.
In step (2), the preparation of intermediate b carries out in dicyandiamide solution, and to the solvent type used, there is no especially limits
It is fixed, as long as raw material can be dissolved and had no adverse effects to reaction.When Z is empty, the solvent used can be alcohol and water
The mixed solvent of mixed solvent, preferred alcohol and water；The reaction carries out under heated reflux condition.When Z is carbonyl, use
Solvent includes but is not limited to one of group of methylene chloride, benzene, toluene and tetrahydrofuran composition or a variety of, and nitrous acid ester includes
But one of it is not limited to the group of nitrous ether (ethyl nitrite), isoamyl nitrite and nitrous acid different monooctyl ester composition or a variety of, nitrite
Including but not limited to sodium nitrite and/or potassium nitrite.
In step (3), esterification carries out in organic solvent, is not particularly limited to solvent type, as long as can
It dissolves raw material and has no adverse effects to reaction, preferably methylene chloride, dichloroethanes, benzene, toluene and dimethylbenzene form
One of group is a variety of.
According to a further aspect of the invention, the present invention also provides a kind of Photocurable composition, the Photocurable composition packets
Containing photoinitiator, photoinitiator includes fluorine-containing fluorenes oxime ester lightlike initiating agent shown in above-mentioned logical formula (I).
In fluorine-containing fluorenes oxime ester lightlike initiating agent provided by the present application, by 9 fluorene structured introducing polymerizable groups, this
Enable formed photoinitiator polymerize with substrate so that the photoinitiator have the advantages that it is not easy to migrate.Together
When due to introducing fluoro-containing group, photoinitiator provided by the present application also has the advantages that efficiency of initiation is high.In addition, in structure
Particularity, which makes the photoinitiator also, has the advantages that surface drying performance is good, surface cure effect is good etc..On this basis, above-mentioned light
Initiator has the advantages that not easy to migrate, efficiency of initiation is high, surface drying performance is good and surface cure effect is good etc..Comprising above-mentioned fluorine-containing
The Photocurable composition of fluorenes oxime ester lightlike initiating agent also has that not easy to migrate, efficiency of initiation is high, surface drying performance is good and surface cure
The advantages that effect is good.
According to a further aspect of the invention, the present invention also provides fluorine-containing fluorenes oxime esters light shown in above-mentioned logical formula (I) to draw
Send out application of the agent in curing field.
In fluorine-containing fluorenes oxime ester lightlike initiating agent provided by the present application, by 9 fluorene structured introducing polymerizable groups, this
Enable formed photoinitiator polymerize with substrate so that the photoinitiator have the advantages that it is not easy to migrate.Together
When due to introducing fluoro-containing group, photoinitiator provided by the present application also has the advantages that efficiency of initiation is high.In addition, in structure
Particularity, which makes the photoinitiator also, has the advantages that surface drying performance is good, surface cure effect is good etc..On this basis, above-mentioned light
Initiator has the advantages that not easy to migrate, efficiency of initiation is high, surface drying performance is good and surface cure effect is good etc., and has wide
Application prospect.
Below with reference to specific embodiment, invention is further described in detail, but should not be construed as to the present invention
The limitation of protection scope.
Prepare embodiment
Embodiment 1
(1) synthesis of intermediate 1a
66.1g intermediate 1a, alchlor 27.0g and methylene chloride 100mL are added into the four-hole boiling flask of 500mL, makes
The temperature of raw material in four-hole boiling flask is down to 0 DEG C with ice-water bath.Then under stiring, 57.0g raw material is added dropwise into above-mentioned raw materials
The mixed solution of 1b and 50mL methylene chloride, while the temperature of reaction system being controlled at 10 DEG C hereinafter, 2h is added dropwise.It is added dropwise
After, continue to stir 2h, liquid phase tracking is reacted to complete.Then above-mentioned reaction system is poured slowly into 400g ice water and 50mL
It is stirring while adding in the dilute hydrochloric acid that concentrated hydrochloric acid (37%) is made into, it is then poured into separatory funnel, separates lower layer's methylene chloride
Layer, and continued to clean water layer with 50mL methylene chloride, merge dichloromethane layer.It is (each with the sodium bicarbonate aqueous solution of 5wt%
150mL, totally 3 times) cleaning dichloromethane layer, then washing dichloromethane layer to pH is in neutrality, with 80g anhydrous magnesium sulfate dry two
Chloromethanes layer rotates methylene chloride reaction mixture, is recrystallized by solvent of methanol after filtering, then do in 80 DEG C of baking ovens
Dry 2h obtains 97.2g intermediate 1a, yield 84wt%, purity 98wt%.Synthetic route is as follows:
Intermediate 1a is confirmed by nuclear magnetic resonance spectroscopy and mass spectrum:
1H-NMR(CDCl3, 500MHz): 1.2885-1.3307 (8H, m), 1.8654-1.9975 (8H, m), 2.3506
(3H, s), 3.8098 (2H, s), 4.9657-5.0342 (4H, m), 5.6786-5.7153 (2H, t), 6.1976 (1H, s),
6.4672-6.8400 (3H, m), 7.2813-7.9503 (7H, m).
MS (m/z): 579 (M+1)+。
(2) synthesis of intermediate 1b
Into 500mL four-hole boiling flask be added 57.9g intermediate 1a, hydroxylamine hydrochloride 7.0g, sodium acetate 8.2g, 100mL ethyl alcohol,
50mL water, 85 DEG C are heated to reflux stopping reaction after stirring 5h, and material is poured into 1000mL large beaker, the stirring of 500mL water is added,
It is extracted using 100mL methylene chloride, the anhydrous MgSO of 30g is added in extract liquor4It is dry, it filters, filtrate decompression is rotated and is removed
Solvent obtains oily dope in revolving bottle, dope is poured into stir in 100mL petroleum ether is precipitated, and filters, obtains white powder
Shape solid, 70 DEG C of baking 5h, obtains intermediate 1b 43.7g, yield 72wt%, purity 98wt%, MS (m/z): 608 (M+1)+.Synthesis
Route are as follows:
(3) synthesis of compound 1
30.4g intermediate 1b, 100mL methylene chloride is added into 250mL four-hole boiling flask, stirs 5min at room temperature, then
5g propionyl chloride is added dropwise, about 30min is added dropwise, and continues to stir 2h, 5%NaHCO is then added3Aqueous solution tune pH value to neutrality,
Separatory funnel separates organic layer, then is washed 2 times with 100mL, the anhydrous MgSO of 20g4It dries, filters back spin and steams solvent, obtain sticky
Shape liquid, recrystallizing methanol obtain white solid powder, and filtering obtains the total 27.2g of compound 1, yield 82%, purity 99%.It closes
It is as follows at route:
1 structure of compound is confirmed by nuclear magnetic resonance spectroscopy and mass spectrum:
1H-NMR(CDCl3, 500MHz): 0.9869-1.0045 (3H, t), 1.2895-1.3347 (8H, m), 1.8678-
1.9668 (8H, m), 2.2678-2.3567 (5H, m), 4.9678-5.0546 (4H, m), 5.6695-5.7206 (2H, m),
6.1996 (1H, s), 6.7846-8.0331 (10H, m).
MS (m/z): 664 (M+1)+。
Embodiment 2
(1) synthesis of intermediate 2a
72.5g intermediate 2a, alchlor 27.0g, methylene chloride 100mL are added into the four-hole boiling flask of 500mL, uses
The temperature of raw material in four-hole boiling flask is down to 0 DEG C by ice-water bath.Then under stiring, 54.5g raw material 2b is added dropwise into above-mentioned raw materials
With the mixed solution of 50mL methylene chloride, while by the temperature of reaction system control 10 DEG C hereinafter, 2h is added dropwise.It is added dropwise
Afterwards, continue to stir 2h, liquid phase tracking is reacted to complete.Then above-mentioned reaction system is poured slowly into 400g ice water and the dense salt of 50mL
It is stirring while adding in the dilute hydrochloric acid that sour (37%) is made into, it is then poured into separatory funnel, separates lower layer's dichloromethane layer,
And continued to clean water layer with 50mL methylene chloride, merge dichloromethane layer, it is (each with the sodium bicarbonate aqueous solution of 5wt%
150mL, totally 3 times) cleaning dichloromethane layer, then washing dichloromethane layer to pH is in neutrality, with 80g anhydrous magnesium sulfate dry two
Chloromethanes layer rotates methylene chloride reaction mixture, is recrystallized by solvent of methanol, then in 80 DEG C of oven dryings after filtering
2h obtains 101.8g intermediate 2a, yield 85wt%, purity 98wt%.Synthetic route is as follows:
Intermediate 2a is confirmed by nuclear magnetic resonance spectroscopy and mass spectrum:
1H-NMR(CDCl3, 500MHz): 2.1489-2.1673 (4H, t), 2.3507 (3H, s), 4.1043-4.1554
(4H, t), 5.7986-6.0521 (4H, m), 6.4207-6.4332 (2H, d), 7.1105-7.8023 (10H, m).
MS (m/z): 599 (M+1)+。
(2) synthesis of intermediate 2b
Hydrochloric acid 10.0g, the isoamyl nitrite of 59.8g intermediate 2a, 37wt% are added into 250mL four-hole boiling flask
11.8g, 100mL tetrahydrofuran stir 5h at normal temperature, stop reaction.Material is poured into 1000mL large beaker, is added
The stirring of 500mL water, is extracted using 100mL methylene chloride, and the anhydrous MgSO of 30g is added in extract liquor4It is dry, it filters, filtrate is subtracted
Pressure revolving removes solvent, obtains oily dope in revolving bottle, and dope is poured into and stirs precipitation in 100mL petroleum ether, filters,
White powdery solids, 70 DEG C of baking 5h obtain intermediate 2b44.8g, yield 75%, purity 98%, MS (m/z): 614 (M+1
)+.Synthetic route is as follows:
(3) synthesis of compound 2
30.7g intermediate 2b, 100mL methylene chloride is added into 250mL four-hole boiling flask, stirs 5min at room temperature, then
6.5g propionic andydride is added dropwise, about 30min is added dropwise, and continues to stir 2h, 5%NaHCO is then added3Aqueous solution tune pH value is into
Property, separatory funnel separates organic layer, then is washed 2 times with 200mL, the anhydrous MgSO of 50g4It dries, filters back spin and steams solvent, obtain viscous
Thick liquid, recrystallizing methanol obtain white solid powder, and filtering obtains product 28.5g, yield 85%, purity 99%.
Synthetic route is as follows:
2 structure of compound is confirmed by nuclear magnetic resonance spectroscopy and mass spectrum:
1H-NMR(CDCl3, 500MHz): 1.0004-1.1049 (3H, t), 2.1497-2.2732 (6H, m), 4.1003-
4.1666 (4H, t), 5.8006-6.1056 (4H, m), 6.4275-6.4365 (2H, d), 7.2809-8.0603 (7H, m).MS
(m/z): 670 (M+1)+。
Embodiment 3
Referring to the method for Examples 1 and 2, there is the compound 3~13 of structure shown in table 1 as the preparation of corresponding raw material.
Table 1
Photoinitiator performance evaluation
By preparing representative light curing resin composition, to the curing rate of photoinitiator shown in formula (I) of the present invention, move
The application performances such as shifting property, surface drying are evaluated, the specific steps are as follows:
(1) it is formulated as follows the light curing resin composition (parts by weight) of composition, is shown in Table 2.
Table 2
Wherein, A:1 in table 1,6- hexanediyl ester.
B: acrylate copolymer [benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 70/
10/20) copolymer (Mv:10000)].
C1: compound 1, C2: compound 2, C3: compound 4, C4: compound 7, C5: compound 11, C6: compound 12.
C7 isC8 is
C9 isC10 is
D1 is butanone (solvent).
(2) curing rate.
Above-mentioned composition is stirred under yellow fluorescent lamp, then feeding is formed a film in PET template using roller coating, is done at 90 DEG C
Dry 2min obtains the film that thickness of dry film is 2 μm.Then above-mentioned film is cooled to room temperature, with high-pressure sodium lamp (exposure type
Number: RW-UV70201, single exposure amount 50mJ/cm2) irradiation, to be exposed to above-mentioned film, make its film-forming.
It is evaluated with curing of coating at the number of the passed through shoe formula exposure bands of cured film, it is more by number, show solidification speed
It spends more undesirable.
(3) migration.
Above-mentioned cured film is shredded, as sample.It weighs 0.5g solidification membrane sample to be placed in 50mL beaker, 4.5mL is added
Methanol, and 30min is dissolved using ultrasonic echography.Resulting solution is moved in 10mL volumetric flask, and sample is continued to use first
Alcohol cleans twice (2mL × 2), pours into volumetric flask, and pipetting 0.1mL toluene with pipette is internal standard compound, and addition methanol is fixed molten, shakes
It shakes uniformly, stands.
Using Japanese Shimadzu LC-20A liquid chromatogram (shim pack column, 150 × 6.0nm, detector SPD-20A, detection
Limit 20ppm, Detection wavelength 254nm), it is used at 25 DEG C, flow velocity 1.0mL/min, mobile phase (vol/vol methanol/water=90/
10), see whether to detect the presence of photoinitiator.Go out the percentage meter of peak area ratio, liquid phase with the liquid phase of opposite toluene
Middle initiator content is higher, illustrates that migration is bigger.
(4) surface drying measures
Using cotton pellet method (GB/T 1728-1979 (1989)) are blown, 1 1cm is put down gently in solidification film surface2Loose degreasing
Cotton balls, with mouth away from cotton balls 15cm featheriness cotton balls in the horizontal direction.
As can blowing away cotton balls, film surface does not stay staple, is denoted as A；
As can blowing away cotton balls, but there are staples for film surface, are denoted as B；
Cotton balls can be such as blown away, C is denoted as；
As can blowing away cotton balls, film surface does not stay staple, as dry tack free, illustrates that the surface drying of film is had excellent performance.
Characterization result is as shown in table 3.
Table 3
It can be seen that the fluorenes oxime esters shown in logical formula (I) of the invention containing polymerizable groups from the test result of table 3
The surface drying of photoinitiator is had excellent performance, and efficiency of initiator height, curing rate are fast in photocuring application, and do not migrate, comprehensive
It closes performance and is substantially better than existing oxime ester lightlike initiating agent product.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of fluorine-containing fluorenes oxime ester lightlike initiating agent, which is characterized in that the photoinitiator has structure shown in logical formula (I):
Wherein, the n indicates 1~4 integer；The m indicates 1~4 integer；
The n R1Separately it is selected from-G- (M ')q, hydrogen, nitro, halogen orM ' table
Show 1~4 integer；Wherein, the G is selected from hetero atom or carbonyl, and the hetero atom is O, N or S, and the M ' is selected from C1~C20's
Linear or branched alkyl group, C3~C8Naphthenic base, C3~C8Naphthenic base replace C1~C10Alkyl, C6~C20Aryl, C1
~C10Alkyl, nitro replace C6~C20The C that aryl, cyano replace6~C20Aryl, C4~C20Heteroaryl, nitro replace
C6~C20The C that heteroaryl or cyano replace6~C20One or more carbon atoms in heteroaryl or the M ' are by described miscellaneous
Atom replaces, and q is 1 or 2；
The R2With the R2' separately it is selected from polymerizable groups；
The Z and Z ' separately indicates empty or carbonyl；
The m R3And m ' the R5Separately selected from fluorine, by one or more fluorine-substituted linear or branched alkyl groups, quilt
One or more fluorine-substituted straight or branched alkoxyls；
The R4With the R6Separately it is selected from C1~C20Linear or branched alkyl group, C3~C20Naphthenic base, C3~C8Ring
Alkyl-substituted C1~C10Alkyl, C1~C10Alkyl-substituted C3~C8Naphthenic base, C6~C20Aryl, C4~C20Heteroaryl
Base or C2~C20Alkenyl.
2. fluorine-containing fluorenes oxime ester lightlike initiating agent according to claim 1, which is characterized in that the M ' is selected from C1~C10It is straight
Chain or branched alkyl, C3~C6Naphthenic base, C3~C6Naphthenic base replace C1~C5Alkyl, C6~C10Aryl, C1~C5
The C that alkyl, nitro replace6~C10The C that aryl, cyano replace6~C10Aryl, C4~C10Heteroaryl, nitro replace C6~
C10The C that heteroaryl or cyano replace6~C10Heteroaryl.
3. fluorine-containing fluorenes oxime ester lightlike initiating agent according to claim 1, which is characterized in that the R2With the R2' only respectively
On the spot it is selected from the polymerizable groups containing double bond or epoxy group.
4. fluorine-containing fluorenes oxime ester lightlike initiating agent according to claim 3, which is characterized in that the R2With the R2' only respectively
On the spot it is selected from C2~C12Alkenyl, alternatively, the R2With the R2' in one or more-CH2Separately by-O-,It is replaced；
Preferably, the R2With the R2' separately it is selected from C3~C8Alkenyl, alternatively, the R2With the R2' in one
A or multiple-CH2Separately by-O-,It is replaced.
5. fluorine-containing fluorenes oxime ester lightlike initiating agent according to claim 3, which is characterized in that the R2With the R2' only respectively
The C on the spot replaced selected from Oxyranyle1~C10The C that alkyl or propylene oxide base replace1~C10Alkyl or the R2And institute
State R2' in C1~C10One or more of alkyl-CH2Each independently by-O-, Or-O-
CH2-CH(OH)-CH2- O- replaces.
6. fluorine-containing fluorenes oxime ester lightlike initiating agent according to claim 5, which is characterized in that the R2With the R2' only respectively
On the spot selected from using Oxyranyle or cyclopropyl alkyl as the C of end-capping group1~C8Alkyl or the R2With the R2' in C1
~C8One or more of alkyl-CH2Each independently by-O-,Or-O-CH2-CH
(OH)-CH2H replaced-O- or in the Oxyranyle or the propylene oxide base is by C1~C4Alkyl replaced.
7. fluorine-containing fluorenes oxime ester lightlike initiating agent according to any one of claim 1 to 4, which is characterized in that the m R3
And a R of m '5Separately selected from F,
8. fluorine-containing fluorenes oxime ester lightlike initiating agent according to any one of claim 1 to 4, which is characterized in that the R4And institute
State R6Separately it is selected from C1~C6Linear or branched alkyl group, C3~C10Naphthenic base, C3~C6The C that naphthenic base replaces1~
C8Alkyl, C1~C8Alkyl-substituted C3~C6Naphthenic base or C6~C12Aryl.
9. fluorine-containing fluorenes oxime ester lightlike initiating agent according to claim 8, which is characterized in that the R4With the R6It is only respectively
On the spot it is selected from phenyl, C1~C4Linear or branched alkyl group, C3~C8Naphthenic base or C3~C6The C that naphthenic base replaces1~C4Alkane
Base.
10. fluorine-containing fluorenes oxime ester lightlike initiating agent according to any one of claim 1 to 9, which is characterized in that described fluorine-containing
Fluorenes oxime ester lightlike initiating agent is selected from
One of group of composition is a variety of.
11. a kind of Photocurable composition, which is characterized in that the Photocurable composition includes photoinitiator, the photoinitiator
Including fluorine-containing fluorenes oxime ester lightlike initiating agent described in any one of claims 1 to 10.
12. fluorine-containing fluorenes oxime ester lightlike initiating agent answering in curing field described in a kind of any one of claims 1 to 10
With.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711415551.4A CN109957046B (en) | 2017-12-22 | 2017-12-22 | Fluorine-containing fluorene oxime ester photoinitiator, photocuring composition containing fluorine-containing fluorene oxime ester photoinitiator and application of fluorine-containing fluorene oxime ester photoinitiator |
| PCT/CN2018/119354 WO2019120081A1 (en) | 2017-12-22 | 2018-12-05 | Photoinitiator containing fluorine fluorene oxime esters, photocurable composition comprising same, and application of photoinitiator |
| KR1020207021061A KR102361560B1 (en) | 2017-12-22 | 2018-12-05 | Fluorine-containing fluorene oxime ester photoinitiators, photocurable compositions comprising same, and uses thereof |
| JP2020534205A JP6999039B2 (en) | 2017-12-22 | 2018-12-05 | Fluorine-containing fluorene oxime ester-based photoinitiator, photo-curing composition containing it, and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711415551.4A CN109957046B (en) | 2017-12-22 | 2017-12-22 | Fluorine-containing fluorene oxime ester photoinitiator, photocuring composition containing fluorine-containing fluorene oxime ester photoinitiator and application of fluorine-containing fluorene oxime ester photoinitiator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109957046A true CN109957046A (en) | 2019-07-02 |
| CN109957046B CN109957046B (en) | 2020-07-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790648A (en) * | 2019-10-24 | 2020-02-14 | 安庆飞凯新材料有限公司 | Polymerisable photoinitiator based on benzanthrone and preparation method thereof |
| CN112341359A (en) * | 2019-08-07 | 2021-02-09 | 常州强力电子新材料股份有限公司 | Fluorenoxime ester compound, preparation method and application thereof |
| CN116097129A (en) * | 2020-08-21 | 2023-05-09 | 富士胶片株式会社 | Compound, curable resin composition, cured product, optical component, and lens |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805955A (en) * | 2004-08-20 | 2006-07-19 | 旭电化工业株式会社 | Oxime ester compound and photopolymerization initiator containing such compound |
| CN101014569A (en) * | 2004-08-18 | 2007-08-08 | 西巴特殊化学品控股有限公司 | Oxime ester initiators |
| JP4948112B2 (en) * | 2006-10-13 | 2012-06-06 | 株式会社Ａｄｅｋａ | Oxime ester compound and photopolymerization initiator containing the compound as an active ingredient |
| EP2845845A4 (en) * | 2012-05-03 | 2015-12-09 | Korea Res Inst Chem Tech | Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same |
| CN106537254A (en) * | 2014-07-15 | 2017-03-22 | 东京应化工业株式会社 | Photosensitive composition and compound |
-
2017
- 2017-12-22 CN CN201711415551.4A patent/CN109957046B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014569A (en) * | 2004-08-18 | 2007-08-08 | 西巴特殊化学品控股有限公司 | Oxime ester initiators |
| CN1805955A (en) * | 2004-08-20 | 2006-07-19 | 旭电化工业株式会社 | Oxime ester compound and photopolymerization initiator containing such compound |
| JP4948112B2 (en) * | 2006-10-13 | 2012-06-06 | 株式会社Ａｄｅｋａ | Oxime ester compound and photopolymerization initiator containing the compound as an active ingredient |
| EP2845845A4 (en) * | 2012-05-03 | 2015-12-09 | Korea Res Inst Chem Tech | Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same |
| CN106537254A (en) * | 2014-07-15 | 2017-03-22 | 东京应化工业株式会社 | Photosensitive composition and compound |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341359A (en) * | 2019-08-07 | 2021-02-09 | 常州强力电子新材料股份有限公司 | Fluorenoxime ester compound, preparation method and application thereof |
| CN112341359B (en) * | 2019-08-07 | 2022-05-06 | 常州强力电子新材料股份有限公司 | Fluorenoxime ester compound, preparation method and application thereof |
| CN110790648A (en) * | 2019-10-24 | 2020-02-14 | 安庆飞凯新材料有限公司 | Polymerisable photoinitiator based on benzanthrone and preparation method thereof |
| CN110790648B (en) * | 2019-10-24 | 2023-02-28 | 安庆飞凯新材料有限公司 | Polymerisable photoinitiator based on benzanthrone and preparation method thereof |
| CN116097129A (en) * | 2020-08-21 | 2023-05-09 | 富士胶片株式会社 | Compound, curable resin composition, cured product, optical component, and lens |
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