CN115124453A - Nitrocarbazole oxime ester photoinitiator for improving solubility by group modification and preparation method thereof - Google Patents
Nitrocarbazole oxime ester photoinitiator for improving solubility by group modification and preparation method thereof Download PDFInfo
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- CN115124453A CN115124453A CN202210828557.9A CN202210828557A CN115124453A CN 115124453 A CN115124453 A CN 115124453A CN 202210828557 A CN202210828557 A CN 202210828557A CN 115124453 A CN115124453 A CN 115124453A
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- oxime ester
- alkyl group
- atoms
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- carbazole oxime
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- -1 Nitrocarbazole oxime ester Chemical class 0.000 title claims abstract description 54
- 230000004048 modification Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000002715 modification method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 238000012986 modification Methods 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 68
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 239000000543 intermediate Substances 0.000 claims description 26
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 22
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 22
- 125000004434 sulfur atom Chemical group 0.000 claims description 22
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Chemical group 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000976 ink Substances 0.000 claims description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000004185 ester group Chemical group 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 229920002120 photoresistant polymer Polymers 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000006146 oximation reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- 238000000016 photochemical curing Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002484 inorganic compounds Chemical class 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 229910000679 solder Inorganic materials 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 claims description 2
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004946 alkenylalkyl group Chemical group 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000008365 aromatic ketones Chemical class 0.000 claims description 2
- 150000001649 bromium compounds Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 206010034972 Photosensitivity reaction Diseases 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 230000036211 photosensitivity Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 4
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HLDHFOCXVJJMBT-UHFFFAOYSA-N 5-methylhexanoyl chloride Chemical compound CC(C)CCCC(Cl)=O HLDHFOCXVJJMBT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- VYOKOQDVBBWPKO-UHFFFAOYSA-N 1-nitro-9h-carbazole Chemical group N1C2=CC=CC=C2C2=C1C([N+](=O)[O-])=CC=C2 VYOKOQDVBBWPKO-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101001061788 Homo sapiens Ras-related protein Rab-35 Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 102100029568 Ras-related protein Rab-35 Human genes 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PKNLWLCURZNADF-UHFFFAOYSA-N hex-5-enoyl chloride Chemical compound ClC(=O)CCCC=C PKNLWLCURZNADF-UHFFFAOYSA-N 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Indole Compounds (AREA)
Abstract
The invention provides a nitro carbazole oxime ester photoinitiator which has a structural general formula as follows,
Description
Technical Field
The invention belongs to the field of new light radiation polymerization materials, and relates to a photopolymerization initiator, in particular to a nitro carbazole oxime ester photoinitiator for improving solubility by utilizing group modification and a preparation method thereof.
Background
Photopolymerization initiators are those which decompose by absorbing light to generate chemically active atoms or molecules, and photosensitive compositions are those obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiating the photosensitive composition with 365nm to 435nm light, and they are widely used as photopolymerization initiators for various compositions such as photocurable inks, photosensitive printing plates, and photoresists.
The light radiation curing is a key technology in the field of new materials, the oxime ester photoinitiator has high photosensitivity, and is widely applied to the fields of high-end photoresists and inks such as color filters (R G B), Black Matrixes (BM), LDI photoresist photosensitive inks, column spacers, organic insulating films, photoresists and the like in color filters CF, so that the novel photopolymerization initiator which meets the requirements of the industrial fields and is suitable for multiple purposes has the characteristics that: the high-sensitivity high-resolution high-solubility light source has high sensitivity and high resolution for long-wavelength light sources such as 365 nm-435 nm, is easy to manufacture, has the advantages of cost and economy, high thermal stability and storage stability, is easy to operate, and has satisfactory solubility for solvents such as Propylene Glycol Monomethyl Ether Acetate (PGMEA). The nitro carbazole oxime ester type photoinitiator disclosed by the invention is optimized and innovated aiming at the scene requirements, and the application of various industrial scenes is remarkably expanded.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a nitro carbazole oxime ester photoinitiator for improving solubility by group modification and a preparation method thereof, and the nitro carbazole oxime ester photoinitiator for improving solubility by group modification and the preparation method thereof aim to solve the technical problems of insufficient solubility and compatibility of the photoinitiator in the prior art.
The invention provides a nitro carbazole oxime ester photoinitiator which has a structural general formula as follows,
wherein R is 1 Is composed of
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (A), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
R 2 is composed of
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (a), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
R 3 is composed of
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (a), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
x is F, Cl, Br, I, mercaptan, N alkyl, hydroxyl or functional aromatic ketone.
Further, R 1 、R 2 And R 3 Satisfies at least one condition satisfying the modification of the flexible molecule group, or R 1 、R 2 And R 3 Two of them simultaneously meet the modification condition of flexible molecular group.
Further, X can be a symmetrical nitro carbazole oxime ester structure, and the structural general formula of the nitro carbazole oxime ester photoinitiator is (II):
wherein R is 2 ' is
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (A), or
Alkenylalkyl of (b), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
R 3 ' is
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (A), or
Alkenylalkyl of (b), or
The alkyl group containing functional aromatic group modification, or the heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or the alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl or ester groups.
Further, R 2 And R 2 ' may be the same or different groups, R 3 And R 3 ' may be the same or different groups.
Further, R 1 The alkyl group is C3-C20 straight chain or branched chain alkyl, or C4-C20 cycloalkyl alkyl, or C3-C20 alkenyl alkyl, or alkyl substituted or interrupted by 1-5 oxygen atoms, nitrogen atoms, silicon atoms or sulfur atoms, and the methylene group of the alkylene part of the alkyl group is interrupted by ether bond or ester bond 1-5 times and is branched alkyl with the carbon number of more than 8.
The invention also provides a preparation method of the nitro carbazole oxime ester photoinitiator, which comprises the following steps:
wherein the content of the first and second substances,
(1) m1 intermediate synthesis by reacting starting material RM with acyl chloride compound R in organic solvent under the catalysis of Lewis acid 2 -CO-Cl or anhydride compound (R) 2 -CO) 2 O is prepared by Friedel-crafts acylation;
(2) the M2 intermediate is prepared by oximation reaction of M1 intermediate under the action of hydroxylamine hydrochloride and sodium acetate;
(3) the target product P is prepared from M2 intermediate and acyl chloride compound R 3 -CO-Cl or anhydride compound (R) 3 -CO) 2 And performing esterification reaction on the O.
Further, the invention also provides a preparation method of the nitro carbazole oxime ester photoinitiator, which is characterized by comprising the following steps:
wherein the content of the first and second substances,
(1) m 'intermediate synthesis is carried out by reacting raw material RM' with acyl chloride compound R in organic solvent under catalysis of Lewis acid 2 ' -CO-Cl or acid anhydride compound (R) 2 ’-CO) 2 Performing Friedel-crafts acylation reaction on O, performing oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate, and finally performing oximation reaction with acyl chloride compound R 3 ' -CO-Cl or acid anhydride compound (R) 3 ’-CO) 2 Performing esterification reaction on O to obtain;
(2) target product P 1 The intermediate is prepared by alkylation reaction of M 'and P' intermediates in an organic solvent; wherein P' is selected from one of the bromides of the general formula (I).
Specifically, the Lewis acid is aluminum trichloride, ferric trichloride or zinc chloride.
Further, the nitro carbazole oxime ester compound is selected from, but not limited to, any one of the following structures:
the invention also provides a photocurable composition, which comprises a polymerizable compound with an alkene unsaturated bond and the nitro carbazole oxime ester photoinitiator according to claim 1, wherein the content of the nitro carbazole oxime ester photoinitiator is 0.01-10 parts by mass relative to 100 parts by mass of the photocurable composition, and the balance is the polymerizable compound with the alkene unsaturated bond.
Further, the above-mentioned photocurable composition further contains an inorganic compound and a solvent.
The solvent is one or the combination of more than two of propylene glycol methyl ether acetate, 1, 2-propylene glycol diacetate, 3-methoxybutyl acetate, propylene glycol methyl ether, ethyl-3-ethoxypropionate or dipropylene glycol monomethyl ether acetate.
The invention also provides application of the nitro carbazole oxime ester photoinitiator in the field of photocuring, wherein the photocuring field is liquid film bodies, dry film bodies, solder resists, color resistors, black matrixes, semiconductor photoresists, LDI electronic ink, column spacers, organic insulating films or photoresists.
According to the invention, by introducing flexible group modification into the nitro carbazole oxime ester structure, the defects of compound solubility and compatibility are effectively overcome, and the oxime ester compound has the advantages of high photosensitive activity, easiness in manufacturing, economic competitiveness, good storage stability, good solvent solubility and dispersity, and therefore has a prominent industrial scene application value.
The application of the nitro carbazole oxime ester compound disclosed by the invention is to serve as an effective photoinitiator in a polymerization process initiated by light radiation in an alkene double bond-containing unsaturated photocurable composition system, and when the compound is used as the photoinitiator, besides the nitro carbazole oxime ester compound disclosed by the invention, other known photoinitiators or sensitizers in the literature can be used according to needs, and a remarkable synergistic effect can be achieved by compounding other photoinitiators or sensitizers.
Wherein the effective component of the alkene double bond containing type unsaturated light curing composition system is 100 parts by mass, and the content of the photoinitiator is 0.01-10 parts by mass. If the content of the photoinitiator is less than 0.01 part by mass, the overall luminous efficiency of the composition system is lowered; the content of the photoinitiator is higher than 10 parts by mass, and the deep curing efficiency of the thick coating is reduced due to the reduction of the photon energy transmittance during the light radiation curing.
Further, the ethylenically double bond-containing unsaturated photocurable composition system may comprise a solvent, preferably ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, or the like, wherein the solvent is preferably an organic solvent having a boiling point of 100 to 200 ℃, preferably: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, xylene, cyclohexanone, butyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and the like.
Further, the ethylenically double bond-containing unsaturated photocurable composition system may contain inorganic compounds, and may be used as fillers, conductive agents, stabilizers, flame retardants, performance strength enhancers, and the like.
Further, the ethylenically double bond-containing unsaturated photocurable composition system may include a system in which the coloring material becomes a colored photosensitive ethylenically double bond-containing unsaturated photocurable composition, particularly RGB ink, BM ink, LDI solder mask ink, and the like.
The compound of the invention has oxime ester compounds with high photosensitivity and excellent solubility, a photopolymerization initiator taking the compound as an active ingredient, and a photosensitive composition formed by containing the photopolymerization initiator in a polymerizable compound with an ethylenic unsaturated bond, and further, in the field of LCD ink, the oxime ester compounds and the photocuring composition containing the oxime ester compounds have the characteristics of excellent photosensitivity, solvent precipitation resistance inhibition (prevention of liquid crystal pollution), ideal absorption waveband and the like; in the LDI photoresist photosensitive ink field, the method has the characteristics of high sensitivity, clean development and good dispersity.
The group modification referred to herein is the introduction of a flexible molecular group into the molecular structure, wherein the flexible molecular group concept is as follows: molecular flexibility is primarily related to the presence of single bonds in the molecule, typically sp3 hybridized C-C bonds. The "free" rotation of atoms around a single bond allows the molecule to adopt different conformations, as the number of single bonds increases, so does the flexibility. Thus, to assess the extent of flexible molecular modification, quantitative assessments of the solvency of such photoinitiators are made herein in the context of industrial applications.
Compared with the prior art, the invention has the advantages of positive and obvious technical effect. According to the invention, by introducing flexible molecular group modification into a nitro carbazole structure, the solubility and the light sensitivity of the compound are effectively improved, the product has high photosensitive activity, good solubility and good storage property, and has the advantages of high sensitivity, foreign matter reject ratio inhibition, clear pattern and the like when being applied to LCD printing ink, and the problem of liquid crystal pollution caused by solvent dissolution of polluted liquid crystal can be solved by inhibiting solvent dissolution. The method is applied to the field of LDI printing ink, has the advantages of high photosensitive efficiency, easy film fading and the like, and is particularly suitable for occasions with extremely high requirements on the photosensitive grade.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not to be construed as limiting the scope of the invention.
Example 1
Synthesis of Compound (I):
adding RM1(35.2g, 100mmol) and aluminum trichloride (15g, 113mmol) into 120mL dichloroethane under the protection of nitrogen, dropwise adding isoheptoyl chloride (16.5g, 110mmol), stirring until the reaction is complete, pouring the reaction solution into 120mL of 1N diluted hydrochloric acid, separating to collect an organic phase,the aqueous phase was extracted with 50mL of dichloroethane, the combined organic phases were dried, desolventized and recrystallized from methanol to yield 39.5g of intermediate M1, 85.1% yield, 99.0% purity, MS (M/z):465.20(M + H) + . Adding intermediate M1(39.5g, 85mmol), hydroxylamine hydrochloride 6g and sodium acetate 6.5g into a mixed solvent of 80mL ethanol and 25mL water, refluxing at 85 ℃ for 6 hours, pouring the reaction solution into 500mL ice water, filtering by suction to collect precipitated solid, and recrystallizing with methanol to obtain 38.7g of intermediate M2 with yield of 95% and purity of 98%, MS (M/z):480.20(M + H) + . Intermediate M2(38.7g, 81mmol), triethylvaleryl chloride (12.5g, 85mmol) were added to 100mL of dichloroethane, triethylamine (9.8g, 97mmol) was added dropwise, the reaction mixture was stirred until the reaction was completed, the reaction mixture was washed with saturated sodium bicarbonate water, dried and desolventized, and methanol was recrystallized to give 44.9g of Compound one, yield 94%, purity 99%, MS (M/z):592.30(M + H) + 。
Compound (i): 1H-NMR (300MHZ, CDCl) 3 )δ:0.90(6H,d)；0.98(6H,m)；1.19(6H,m)；1.39(2H,m)；1.73(2H,m)；1.91(2H,m)；2.13(2H,d)；2.68(2H,t)；3.32(2H,t)；3.78(2H,dd)；4.12(2H,t)；7.72(1H,d)；7.85(1H,d)；8.05(1H,d)；8.13(1H,d)；8.76(1H,s)；8.82(1H,s)。
Example 2
Synthesis of Compound (II)
Adding RM1(64g, 200mmol) and aluminum trichloride (26.7g, 220mmol) into 300mL dichloroethane under the protection of nitrogen, dropwise adding isoheptoyl chloride (33g, 220mmol), stirring until the reaction is complete, pouring the reaction solution into 250mL of 1N diluted hydrochloric acid, separating, collecting organic phase, extracting aqueous phase with 100mL dichloroethane, combining organic phases, drying, desolventizing, recrystallizing with methanol to obtain 75.7g of intermediate M1 with yield of 88%, purity of 99.0%, MS (M/z):432.1(M + H) + . Intermediate M1(43g, 100mmol), hydroxylamine hydrochloride 10g, and sodium acetate 12g were added to a mixed solvent of 120mL of ethanol and 40mL of water, and the mixture was refluxed at 85 ℃ for 6 hours, and then the reaction solution was poured into 600mL of ice water, followed by suction filtrationThe precipitated solid was collected and recrystallized from methanol to give 42.3g of intermediate M2, 95% yield, 98% purity, MS (M/z):447.10(M + H) + . Intermediate M2(40g, 90mmol), 5-hexenoyl chloride (13g, 99mmol) were added to 150mL dichloroethane, triethylamine (11g, 109mmol) was added dropwise, the reaction was stirred until the end of the reaction, the reaction mixture was washed with saturated sodium bicarbonate water, dried and desolventized, and then recrystallized from methanol to obtain 45.8g of Compound one, yield 94%, purity 99%, MS (M/z):543.16(M + H) + 。
Compound (ii): 1H-NMR (300MHZ, CDCl) 3 )δ:0.91(6H,d)；1.18(2H,q)；1.45(2H,m)；1.62(3H,m)；2.16(2H,q)；2.32(2H,t)；2.71(2H,t)；3.34(3H,t)；4.38(3H,t)；4.85(H,d)；5.22(H,d)；5.84(1H,m)；7.83(1H,d)；7.86(1H,d)；8.13(1H,d)；8.21(1H,d)；8.84(1H,s)；8.91(1H,s)。
Example 3
Synthesis of Compound (III)
Adding RM1(54g, 200mmol) and zinc chloride (30g, 220mmol) into 300mL dichloroethane under the protection of nitrogen, dropwise adding hexanoyl chloride (29.5g, 220mmol), stirring until the reaction is complete, pouring the reaction solution into 300mL 1N sodium hydroxide, stirring until the reaction is clear, separating to collect an organic phase, extracting an aqueous phase with 150mL dichloroethane, combining the organic phases, drying, desolventizing and recrystallizing with methanol to obtain 77.4g of intermediate M1, wherein the yield is 93%, the purity is 99.0%, and MS (M/z):418.07(M + H) + . Adding intermediate M1(42g, 100mmol), hydroxylamine hydrochloride 10g and sodium acetate 12g into a mixed solvent of 120mL ethanol and 40mL water, refluxing at 85 ℃ for 6 hours, pouring the reaction solution into 600mL ice water, filtering by suction, collecting the precipitated solid, and recrystallizing with methanol to obtain 42g intermediate M2 with yield of 97% and purity of 98%, MS (M/z):433.08(M + H) + . Adding intermediate M2(42g, 97mmol) and epoxy propionyl chloride (11g, 102mmol) into 150mL dichloroethane, dropwise adding triethylamine (11g, 109mmol), stirring until the reaction is finished, washing the reaction solution with saturated sodium bicarbonate water, drying, desolventizing, and recrystallizing with methanol to obtain the final product41.6g of Compound (II), yield 95%, purity 99%, MS (M/z):452.18(M + H) + 。
Compound (ii): 1H-NMR (300MHZ, CDCl) 3 )δ:0.89(3H,t)；1.26(4H,m)；1.45(2H,m)；2.42(4H,m)；2.56(3H,m)；3.32(1H,t)；3.79(1H,q)；4.04(1H,q)；7.81(1H,d)；7.96(1H,d)；8.06(1H,d)；8.15(1H,d)；8.84(1H,s)；8.88(1H,s)。
Example 4: evaluation of Performance
4.1 dissolution Performance test
Taking Propylene Glycol Methyl Ether Acetate (PGMEA) and N-methyl pyrrolidone (NMP) as the reactive diluents widely used in the field as examples, the photoinitiator of the invention is evaluated by taking the maximum weight soluble in I00g solvent at 20 ℃ as an evaluation standard. The structures of the first and second comparative examples are shown in Table 1.
TABLE 1
| Sample and comparative example | PGMEA(g/100g) | NMP(g/100g) |
| Example one (Compound one) | ＞15 | 12 |
| Example two (Compound two) | ＞15 | 13 |
| EXAMPLE III (Compound III) | ＞15 | 13 |
| Comparative example 1 | Hardly dissolved | 1 |
| Comparative example II | Hardly dissolved | 3 |
From the results of table 1, it was confirmed that the photocurable compositions of examples one, two and three using the oxime ester compound of the present invention as a photopolymerization initiator had competitive solubility properties as compared with the photocurable compositions of comparative examples one and two, and the examples all satisfied excellent solubility properties of 8% solubility required for production in industrial application scenes
4.2 storage stability and film Forming Properties test
Storage stability and film formation properties of compositions one to three formulated with the photoinitiators shown in the present invention were compared and evaluated with those of composition four formulated with the existing commercial photoinitiator OXE-02 by formulating comparative photocurable compositions.
4.2.1 method of formulating Photocurable compositions
Composition one: 200 g of an acrylate copolymer (prepared by mixing methacrylic acid/hydroxyethyl methacrylate/benzyl methacrylate at a molar ratio of 1/2/5), 100 g of dipentaerythritol hexaacrylate, 900 g of propylene glycol methyl ether acetate as a reactive diluent and 5g of the compound one of example one were mixed and dispersed at high speed for 1 hour, thereby obtaining a composition one;
composition II: 200 g of an acrylate copolymer (prepared by mixing methacrylic acid/hydroxyethyl methacrylate/benzyl methacrylate at a molar ratio of 1/2/5), 100 g of dipentaerythritol hexaacrylate, 900 g of propylene glycol methyl ether acetate as a reactive diluent, and 5g of the compound two of example two were mixed and dispersed at a high speed for 1 hour, thereby obtaining a composition two;
composition III: 200 g of an acrylate copolymer (prepared by mixing methacrylic acid/hydroxyethyl methacrylate/benzyl methacrylate at a molar ratio of 1/2/5), 100 g of dipentaerythritol hexaacrylate, 900 g of propylene glycol methyl ether acetate as a reactive diluent, and 5g of compound III of example III were mixed and dispersed at high speed for 1 hour, thereby obtaining composition III;
composition four: 200 g of an acrylate copolymer (prepared by mixing methacrylic acid/hydroxyethyl methacrylate/benzyl methacrylate at a molar ratio of 1/2/5), 100 g of dipentaerythritol hexaacrylate, 900 g of propylene glycol methyl ether acetate as a reactive diluent, and 5g of tris (OXE-02) as a comparative example were mixed and dispersed at high speed for 1 hour, thereby obtaining a composition IV;
4.2.2 storage stability
After the compositions one, two, three and four were naturally stored at room temperature for 1 month, the stability of the substances was evaluated by visual observation according to the following criteria, and the test results are shown in table 2
A: no precipitation was observed
B: slight precipitation was observed
C: significant precipitation was observed
TABLE 2
| Test example | Storage stability |
| Composition I | A |
| Composition II | A |
| Composition III | A |
| Composition IV | B |
From the results of Table 2, it was confirmed that the photocurable compositions of composition I, composition II and composition III using the oxime ester compound of the present invention as a photopolymerization initiator had better storage stability than composition IV prepared using a commercially available photoinitiator OXE-02.
4.2.3 film Forming Properties
Coating the composition on an aluminum substrate with a thickness of 1 μm, prebaking at 65 ℃ for 15 minutes, exposing with a 250W ultra-high pressure mercury lamp as a light source, realizing long-wavelength radiation of 365nm I-ray and 405nm H-ray through a FWHM filter, then soaking in 2.5% sodium carbonate solution at 25 ℃ for development, washing with deionized water, air-drying, postbaking at 220 ℃ for 20 minutes to fix the image, and evaluating the obtained pattern in terms of sensitivity, hardness, developability, image color formation, and the like, respectively:
1. sensitivity to light: the minimum curing energy at which the film-forming residual rate after development of the light-irradiated region in the exposure process is 90% or more is defined as the exposure demand, and a smaller exposure demand represents a higher photosensitivity. The results of the evaluation of photosensitivity are shown in Table 3.
TABLE 3
Where it can be concluded from table 3: the photosensitive compositions of the first, second and third compositions have excellent photosensitivity to light with 365nm and 405nm wavelengths, but the photosensitive composition of the fourth composition has poorer photosensitivity to light with 365nm and 405nm wavelengths and requires more severe exposure energy compared with the first three compositions.
2. Hardness: the four groups of photosensitive compositions were coated on a substrate with a 30 μm wire bar, irradiated with 100W high-pressure mercury lamp for 45 seconds, cured, and then placed in an oven at 70 ℃ for baking for 2 hours, and then the pencil hardness was measured with a pencil hardness tester at a load weight of two pounds. The results of the pencil hardness test are shown in table 4.
TABLE 4
| Test example | Hardness of pencil |
| Composition I | 3H |
| Composition II | 3H |
| Composition III | 3H |
| Composition IV | 1H |
Where it can be concluded from table 4: in the test examples, the hardness of composition one, composition two and composition three was higher, compared to the hardness of composition four, which was lower and could not meet the hardness requirement in the industrial application scenario.
3. Development performance and image resolution: the image of the substrate was observed with a Scanning Electron Microscope (SEM) to evaluate the developability and image analysis.
Wherein the development performance is according to the following evaluation criteria:
and (3) excellent: no residue was observed in the unexposed parts;
good: no small amount of residue was observed in the unexposed parts and the overall development performance was acceptable;
difference: no significant residue was observed in the unexposed parts, affecting the overall development performance;
wherein the image resolution is according to the following evaluation criteria:
and (3) optimization: through observation, no image analysis defect is found;
good: through observation, a few of images have defects in analysis, and the integral image resolution is not influenced;
difference: through observation, the image analysis has obvious defects, which affects the image resolution;
the evaluation results are shown in Table 5.
TABLE 5
| Test example | Development Properties | Image resolution |
| Composition I | Good wine | Superior food |
| Composition II | Superior food | Superior food |
| Composition III | Superior food | Superior food |
| Composition IV | Good quality | Difference (D) |
Where it can be concluded from table 4: compared with the prior oxime ester photoinitiator, the composition I, the composition II and the composition III prepared by the photoinitiator shown in the patent have more excellent developing performance and higher image resolution, and the composition IV prepared by the commercial photoinitiator OXE-02 has poorer competitive power of developing performance and image resolution performance.
In conclusion, the oxime ester compound disclosed by the invention has excellent solubility, so that the oxime ester compound is very beneficial to the physical and chemical performance requirements on the compatibility and compatibility of a formula system in an industrial application scene; in addition, the oxime ester compound has excellent photosensitivity, image resolution and the like, and particularly has excellent sensitivity to 365nm (I line) and 405nm (H line) with long wavelength, so that the oxime ester compound has wider application and wider applicability in the field of photoresist.
It is emphasized that the above-listed compounds are merely some preferred exemplary structures and should not be considered as limiting structures or limiting the invention. Various modifications and alterations to this invention will become apparent to 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 (12)
1. A nitro carbazole oxime ester photoinitiator is characterized in that the structural general formula is as follows,
wherein R is 1 Is composed of
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (a), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
R 2 is composed of
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (A), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
R 3 is composed of
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (A), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
x is F, Cl, Br, I, mercaptan, N-alkyl, hydroxyl or functional aromatic ketone.
2. The nitrocarbazole oxime ester photoinitiator according to claim 1, wherein R is 1 、R 2 And R 3 Satisfies at least one condition satisfying the modification of the flexible molecule group, or R 1 、R 2 And R 3 Wherein at most two of the flexible molecule groups simultaneously satisfy the modification condition of the flexible molecule group.
3. The nitro carbazole oxime ester photoinitiator according to claim 1, wherein X can be a symmetrical nitro carbazole oxime ester structure, and the structural general formula of the nitro carbazole oxime ester photoinitiator is (II):
wherein R is 2 ' is
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (A), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or a heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or an alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl groups or ester groups;
R 3 ' is
A linear or branched alkyl group of (a), or
Cycloalkylalkyl of (a), or
Alkenylalkyl of (A), or
The alkyl group containing functional aromatic group modification, or the heterocyclic group containing oxygen atom, sulfur atom or nitrogen atom, or the alkyl group substituted or interrupted by 1-4 oxygen atoms, nitrogen atoms, silicon atoms, sulfur atoms, carboxyl or ester groups.
4. The nitrocarbazole oxime ester photoinitiator according to claim 3, wherein R is 2 And R 2 ' may be the same or different groups, R 3 And R 3 ' may be the same or different groups.
5. A process as claimed in claim 3The nitro carbazole oxime ester photoinitiator is characterized in that R 1 The alkyl group is C3-C20 straight chain or branched chain alkyl, or C4-C20 cycloalkyl alkyl, or C3-C20 alkenyl alkyl, or alkyl substituted or interrupted by 1-5 oxygen atoms, nitrogen atoms, silicon atoms or sulfur atoms, and the methylene group of the alkylene part of the alkyl group is interrupted by ether bond or ester bond 1-5 times and is branched alkyl with the carbon number of more than 8.
6. The method for preparing the nitro carbazole oxime ester photoinitiator according to claim 1, which comprises the following steps:
wherein the content of the first and second substances,
(1) m1 intermediate synthesis is carried out by reacting raw material RM with acyl chloride compound R in organic solvent under catalysis of Lewis acid 2 -CO-Cl or acid anhydride compound (R) 2 -CO) 2 O is prepared by Friedel-crafts acylation;
(2) the M2 intermediate is prepared by oximation reaction of M1 intermediate under the action of hydroxylamine hydrochloride and sodium acetate;
(3) the target product P is prepared from M2 intermediate and acyl chloride compound R 3 -CO-Cl or anhydride compound (R) 3 -CO) 2 And performing esterification reaction on the O.
7. The preparation method of the nitro carbazole oxime ester photoinitiator according to claim 3, which is characterized by comprising the following steps:
wherein the content of the first and second substances,
(1) m 'intermediate synthesis is carried out by reacting raw material RM' with acyl chloride compound R in organic solvent under catalysis of Lewis acid 2 ' -CO-Cl or acid anhydride compound (R) 2 ’-CO) 2 Performing Friedel-crafts acylation reaction on O, performing oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate, and finally performing oximation reaction with acyl chloride compound R 3 ' -CO-Cl or acid anhydride compound (R) 3 ’-CO) 2 Performing esterification reaction on O to obtain;
(2) target product P 1 The intermediate is prepared by alkylation reaction of M 'and P' intermediates in an organic solvent; wherein P' is selected from one of the bromides of the general formula (I).
8. The nitro carbazole oxime ester photoinitiator according to claim 1, wherein the nitro carbazole oxime ester compound is selected from, but not limited to, any of the following structures:
9. a photocurable composition characterized by: the photocurable composition contains a polymerizable compound having an olefinic unsaturated bond and the nitro carbazole oxime ester photoinitiator according to claim 1, wherein the content of the nitro carbazole oxime ester photoinitiator is 0.01 to 10 parts by mass per 100 parts by mass of the photocurable composition, and the balance is the polymerizable compound having an olefinic unsaturated bond.
10. The photocurable composition according to claim 9, wherein: also contains inorganic compound and solvent.
11. The photocurable composition according to claim 10, wherein: the solvent is any one or the combination of more than two of propylene glycol methyl ether acetate, 1, 2-propylene glycol diacetate, 3-methoxybutyl acetate, propylene glycol methyl ether, ethyl-3-ethoxypropionate or dipropylene glycol monomethyl ether acetate.
12. The use of the nitro carbazole oxime ester photoinitiator according to claim 1 in the field of photocuring, wherein the photocuring is liquid film bodies, dry film bodies, solder resists, color resistors, black matrixes, semiconductor photoresists, LDI electronic inks, column spacers, organic insulating films or photoresists.
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| JP2015001654A (en) * | 2013-06-17 | 2015-01-05 | 東レ株式会社 | Method for manufacturing laminate resin black matrix substrate |
| KR20170009794A (en) * | 2015-07-17 | 2017-01-25 | 타코마테크놀러지 주식회사 | Oxime ester compound and photosensitive resin composition containing the compound |
| CN106444282A (en) * | 2015-08-13 | 2017-02-22 | 常州强力先端电子材料有限公司 | Photosensitive resin composition containing oxime ester photoinitiator and application of photosensitive resin composition |
| CN106933032A (en) * | 2015-12-29 | 2017-07-07 | 奇美实业股份有限公司 | Black photosensitive resin composition and application thereof |
| CN108395394A (en) * | 2017-02-06 | 2018-08-14 | 东友精细化工有限公司 | Oxime ester based compound and the Photocurable composition for including the oxime ester based compound |
| CN111132963A (en) * | 2017-10-30 | 2020-05-08 | 株式会社艾迪科 | Compound, composition, cured product, and method for producing cured product |
| KR20210152189A (en) * | 2020-06-08 | 2021-12-15 | 인오켐 주식회사 | Oxime ester carbazole compound,and photosensitive resin composition containing thereof |
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