CN103833872A - 一种双肟酯类光引发剂及其制备方法和应用 - Google Patents
一种双肟酯类光引发剂及其制备方法和应用 Download PDFInfo
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- CN103833872A CN103833872A CN201410100523.3A CN201410100523A CN103833872A CN 103833872 A CN103833872 A CN 103833872A CN 201410100523 A CN201410100523 A CN 201410100523A CN 103833872 A CN103833872 A CN 103833872A
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- group
- oxime ester
- cycloalkylalkyl
- nitrite
- cycloalkyl
- Prior art date
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- Granted
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- 238000002360 preparation method Methods 0.000 title claims description 23
- -1 oxime ester Chemical class 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 230000000977 initiatory effect Effects 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006146 oximation reaction Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 206010034960 Photophobia Diseases 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-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
- 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 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
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- 239000012044 organic layer Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SZQVEGOXJYTLLB-UHFFFAOYSA-N 3-cyclopentylpropanoyl chloride Chemical compound ClC(=O)CCC1CCCC1 SZQVEGOXJYTLLB-UHFFFAOYSA-N 0.000 description 1
- ZIEVFLGQZXYLRV-UHFFFAOYSA-N 3-cyclopropylpropanoyl chloride Chemical compound ClC(=O)CCC1CC1 ZIEVFLGQZXYLRV-UHFFFAOYSA-N 0.000 description 1
- LBDSJNPSTSMQPM-UHFFFAOYSA-N 4-cyclopentylbutanoyl chloride Chemical compound ClC(=O)CCCC1CCCC1 LBDSJNPSTSMQPM-UHFFFAOYSA-N 0.000 description 1
- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Classifications
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C—CHEMISTRY; METALLURGY
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
- C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/63—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
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- 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
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D311/82—Xanthenes
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- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
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- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
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- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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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- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials For Photolithography (AREA)
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- Polymerisation Methods In General (AREA)
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- Pyrane Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明公开一种如通式(I)所示的双肟酯类光引发剂,通过在化学结构中引入双肟酯基团,该光引发剂不仅在储存稳定性、感光度、显影性和图案完整性等方面性能优异,而且与同类光引发剂相比,产品表现出了明显提高的感光度和热稳定性。
Description
技术领域
本发明属于光引发剂技术领域,特别涉及一种双肟酯类光引发剂及其制备方法和应用。
背景技术
具有肟酯结构的化合物在本领域中用作光引发剂已被广泛知悉,如公开号为CN99108598A、CN101508744A、CN10565472A、CN103293855A等专利文献公开了不同的咔唑肟酯和酮肟酯类光引发剂,这些公开的光引发剂可在不同程度上满足当前显示面板及彩色滤光片等光固化领域的一般性应用要求。
但是,电子科技的发展日新月异,已有产品在一些应用领域中开始显现不足,产品的更新换代也对光引发剂提出了更高要求。例如,目前应用于间隙控制材料的光致蚀剂多耐热性不佳,烘烤或封装制程时容易塌陷使得间隙材料缩水,而在涂布、曝光显影等制程中刻意加大间隙控制材料的高度会增加其成本,受热塌陷时热融出的小分子将会污染液晶。又如,在高端彩色滤光片的制作中,一方面光引发剂需满足高溶解性、热稳定性良好的基本要求,另一方面,其高色彩的质量性能要求需经高度着色的抗蚀剂,而随着颜料含量的增加,色彩抗蚀剂的固化变得更加困难,其固化后图像的清晰度、完整度也都有较高的要求,这就需要更高感光度的引发剂来解决上述问题。
在光固化领域中,具有高感光性、稳定性高、且易于制备的光引发剂仍是该领域的发展首选,而研究和开发具有更高性能的光引发剂将一直是该领域的一项核心工作。
发明内容
本发明的目的在于提供一种应用性能优异的双肟酯类光引发剂。通过在化学结构中引入双肟酯基团,该光引发剂不仅在储存稳定性、感光度、显影性和图案完整性等方面性能优异,而且与同类光引发剂相比,表现出了明显提高的感光度和热稳定性。
为了达到上述技术效果,本发明采用的技术方案如下:
一种双肟酯类光引发剂,其具有如通式(I)所示结构:
其中,
R1为其中,*表示连接位,X为空(即,左右两个苯环仅通过Y彼此相连)、单键、或C1-C5的亚烷基基团;Y为O、S或R5N-基团,其中R5为氢、C1-C20的直链或支链烷基、C3-C20环的烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基;
R2、R3相互独立地表示为C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基,任选地,上述基团中的氢可以被选自卤素、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团取代;条件是,R2和R3中至少一个是未被取代或被一个或多个选自卤素、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团取代的环烷基烷基,所述环烷基烷基的结构为其中n为1-5的整数,m为1-6的整数;
R4表示为C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C3-C20的杂芳基、C6-C20的芳基,任选地,上述基团中的氢可以被选自卤素、苯基、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团所取代。
作为本发明的优选方案,上述通式(I)所示的双肟酯类光引发剂中:
R1中,X为空、单键、亚甲基、亚乙基或亚丙基;Y为O、S或R5N-基团,其中R5为氢、C1-C10直链或支链烷基;
R2、R3相互独立地表示为C1-C5的直链或支链烷基、C4-C15的环烷基烷基,任选地,上述基团中的氢可以被选自卤素、硝基、氰基和烷氧基的基团取代;条件是,R2和R3中至少一个是未被取代或被一个或多个选自卤素、硝基、氰基和烷氧基的基团取代的环烷基烷基,所述环烷基烷基的结构为其中n为1-5的整数,m为1-3的整数;
R4表示为C1-C5的直链或支链烷基、C3-C8的环烷基、C4-C8的环烷基烷基、C4-C8的烷基环烷基、C3-C5的杂芳基、C6-C10的芳基,任选地,上述基团中的氢可以被选自卤素、硝基和烷氧基的基团所取代。
进一步优选地,R1选自以下结构:
本发明还涉及上述通式(I)所示的双肟酯类光引发剂的制备方法,包括以下步骤:
式中Z代表卤素,如F、Cl、Br或I;
(2)中间体2的合成:将中间体1在氯化氢、醇钠或醇钾的作用下与亚硝酸酯(如:***、亚硝酸异戊酯、亚硝酸异辛酯等)或亚硝酸盐(如亚硝酸钠、亚硝酸钾等)进行肟化反应,生成中间体2,反应式如下所示:
(3)双肟酯类光引发剂的合成:将中间体2与含有R4基团的酰卤化合物或酸酐进行酯化反应,合成双肟酯类光引发剂产品,反应式如下所示:
式中Z代表卤素,如F、Cl、Br或I。
上述制备方法中,使用的原料均是现有技术中的已知化合物,可商业购得或者通过已知的合成方法制备而成。该制备方法简单,制备过程中不产生污染性废弃物,且产品纯度高,适用于工业化批量生产。
本发明还涉及上述通式(I)所示的双肟酯类光引发剂在光固化组合物(即感光性组合物)中的应用。非限制性地,该光引发剂可应用在彩色光阻(RGB)、黑色光阻(BM)、空间障碍物(Photo-spacer)、干膜、半导体光刻胶及油墨等方面。
具体实施方式
以下将结合具体实施例对本发明作进一步说明,但不应将其理解为对本发明保护范围的限制。
制备实施例
实施例1:
双-{[4-(3-环戊基-1,2-二酮-2-肟-O-丙酸酯)丙基]亚苯基}-硫醚的制备
步骤(1):双-{[4-(3-环戊基-1-酮)丙基]亚苯基}-硫醚的制备
向500mL的四口烧瓶中投入18.6g二苯硫醚、29.4gAlCl3(研细)、100mL二氯甲烷,搅拌,冰浴冷却,当温度降至0℃时,开始滴加33.7g环戊基丙酰氯与50g二氯甲烷的混合液,温度控制在10℃以下,约1.5h加完,继续搅拌2h,停止反应。将反应液倒入400g冰与65mL浓盐酸配成的稀盐酸中,用分液漏斗分出下层料液,上层用50mL二氯甲烷萃取,萃取液与料液合并,用10gNaHCO3和200g水配成的NaHCO3溶液洗涤,再用200mLl水洗涤3次,至pH值呈中性,用30g无水MgSO4干燥除水,旋蒸出二氯甲烷,蒸完后,旋蒸瓶中粗产品呈淡黄色液体,倒入200mL常压蒸过的石油醚中,搅拌、抽滤,得白色粉末状固体,50℃烘箱中烘5h,得产品39.1g,收率90%,纯度96.2%。
步骤(1)产物结构通过核磁共振氢谱得到确认,具体表征结果如下:
1H-NMR(CDCl3,500MHz):1.4274-1.5412(22H,m),2.5214-2.6276(4H,t),7.2738-7.3818(4H,d),7.7908-7.9824(4H,d)。
步骤(2):双-{[4-(3-环戊基-1,2-二酮-2-肟)丙基]亚苯基}-硫醚的制备
向250mL四口烧瓶中投入步骤(1)产物21.7g、四氢呋喃100mL、浓盐酸13.2g和亚硝酸异戊酯11.8g,常温搅拌5h,停止反应;将物料倒入2000mL大烧杯中,加入1000mL水搅拌,使用200g二氯甲烷萃取,在萃取液中加入50g无水MgSO4干燥,抽滤,将滤液减压旋蒸除去溶剂,旋转瓶中得到油状粘稠物,将粘稠物倒入150mL石油醚中搅拌析出,抽滤,得白色粉末状固体,60℃烘5h,得产品20.9g,收率85%,相对纯度95.2%。
步骤(2)产物结构通过核磁共振氢谱得到确认,具体表征结果如下:
1H-NMR(CDCl3,500MHz):1.4037-1.5431(18H,m),2.0321-2.1735(2H,s),2.5001-2.7221(4H,d),7.3034-7.3241(4H,d),7.8002-7.9922(4H,m)。
步骤(3):双-{[4-(3-环戊基-1,2-二酮-2-肟-O-丙酸酯)丙基]亚苯基}-硫醚的制备
向250mL四口烧瓶中投入步骤(2)产物19.7g、100g二氯甲烷、和4.1g三乙胺,室温下搅拌5min,然后滴加7.8g丙酰氯,约30min滴加完毕,继续搅拌2h,然后加入5%NaHCO3水溶液调pH值至中性,分液漏斗分出有机层,再用200mL水洗2遍,50g无水MgSO4干燥,旋转蒸出溶剂,得粘稠状液体,甲醇重结晶得到白色固体粉末,过滤,得产品23.1g,纯度99%。
最终产物结构通过核磁共振氢谱得到确认,具体表征结果如下:
1H-NMR(CDCl3,500MHz):0.9351-1.1213(6H,t),1.3351-1.4913(18H,m),2.1737-2.2923(4H,m),2.6981-2.8821(4H,m),7.3201-8.1241(8H,d)。
实施例2:
[2-(3-环丙基-1,2-二酮-2-肟-O-丙酸酯)丙基]-[7-(4-环戊基-1,2-二酮-2-肟-O-丙酸酯)丁基]-噻吨的制备
步骤(1):[2-(3-环丙基-1-酮)丙基]-[7-(4-环戊基-1-酮)丁基]-噻吨的制备
向500mL的四口烧瓶中投入19.8g噻吨、14.7gAlCl3(研细)、100mL二氯甲烷,搅拌,冰浴冷却,当温度降至0℃时,开始滴加13.5g环丙基丙酰氯与25g二氯甲烷的混合液,温度控制在10℃以下,约1.5h加完,继续搅拌2h,然后向四口烧瓶中加入14.7gAlCl3(研细),滴加17.8g环戊基丁酰氯与25g二氯甲烷的混合液,温度控制在10℃以下,约1.5h加完,温度升至15℃,继续搅2h,停止反应。将反应液倒入400g冰与65mL浓盐酸配成的稀盐酸中,用分液漏斗分出下层料液,上层用50mL二氯甲烷萃取,萃取液与料液合并,用10gNaHCO3和200g水配成的NaHCO3溶液洗涤,再用200mL水洗涤3次,至pH值呈中性,用30g无水MgSO4干燥除水,旋蒸出二氯甲烷,蒸完后,旋蒸瓶中粗产品呈淡黄色液体,倒入200mL常压蒸过的石油醚中,搅拌、抽滤,得白色粉末状固体,50℃烘箱中烘5h,得产品38.1g,收率88%,纯度96.2%。
步骤(1)产物结构通过核磁共振氢谱得到确认,具体表征结果如下:
1H-NMR(CDCl3,500MHz):0.19366-0.2114(5H,m),1.2744-1.5831(15H,m),2.5762-2.6144(4H,t),3.7659-3.8407(2H,s),7.1908-7.2824(2H,d),7.4457-7.5763(4H,m)。
步骤(2):[2-(3-环丙基-1,2-二酮-2-肟)丙基]-[7-(4-环戊基-1,2-二酮-2-肟)丁基]-噻吨的制备
向250mL四口烧瓶中投入步骤(1)产物21.6g、四氢呋喃100mL、浓盐酸13.2g和亚硝酸异戊酯11.8g,常温搅拌5h,停止反应;将物料倒入2000mL大烧杯中,加入1000mL水搅拌,使用200g二氯甲烷萃取,在萃取液中加入50g无水MgSO4干燥,抽滤,将滤液减压旋蒸除去,旋转瓶中得到油状粘稠物,将粘稠物倒入150mL石油醚中搅拌析出,抽滤,得白色粉末状固体,60℃烘5h,得产品21.1g,收率86%,相对纯度95.2%。
步骤(2)产物结构通过核磁共振氢谱得到确认,具体表征结果如下:
1H-NMR(CDCl3,500MHz):0.2037-0.2431(5H,m),1.4355-1.5032(11H,m),2.0117-2.1349(2H,s),2.5132-2.7065(4H,m),3.8002(2H,s),7.3034-7.5241(6H,d)。
步骤(3):[2-(3-环丙基-1,2-二酮-2-肟-O-丙酸酯)丙基]-[7-(4-环戊基-1,2-二酮-2-肟-O-丙酸酯)丁基]-噻吨的制备
向250ml四口烧瓶中投入步骤(2)产物19.6g、100g二氯甲烷、和4.1g三乙胺,室温下搅拌5min,然后滴加7.6g丙酰氯,约30min滴加完毕,继续搅拌2h,然后加入5%NaHCO3水溶液调pH值至中性,分液漏斗分出有机层,再用200mL水洗2遍,50g无水MgSO4干燥,旋转蒸出溶剂,得粘稠状液体,甲醇重结晶得到白色固体粉末,过滤,得产品22.1g,纯度99%。
最终产物结构通过核磁共振氢谱得到确认,具体表征结果如下:
1H-NMR(CDCl3,500MHz):0.1981-0.2209(5H,m),1.1038-1.2004(6H,m),1.498-1.5703(11H,m),2.2765-2.3951(4H,m),2.5964-2.7123(4H,m),3.8678(2H,s),7.2854-7.3409(2H,d),7.3988-7.5028(4H,m)。
实施例3-13:
参照实施例1或2的方法,由与相应的酰化试剂制备实施例3-13所示的化合物。
目标产物的结构及其1H-NMR数据列于表1:
表1
性能评价
通过配制示例光固化组合物,对本发明通式(Ⅰ)所示光引发剂的各项应用性能进行评价,包括储存稳定性、感光度、显影性、图案完整性、热稳定性等方面。
1.光固化组合物的配制
(1)未着色的光固化组合物A
丙烯酸酯共聚物 100
(甲基丙烯酸卞酯/甲基丙烯酸/甲基丙烯酸羟乙酯(摩尔比为70/10/20)共聚物(Mw:10,000))
(甲基丙烯酸卞酯/甲基丙烯酸/甲基丙烯酸甲酯(摩尔比为50/15/30)共聚物(Mw:15,000))
上述组合物A和B中,光引发剂为本发明公开的通式(Ⅰ)所示的双肟酯类化合物或作为对比的现有技术中已知的光引发剂,各组分均为质量份。
2.曝光显影
将上述的光固化组合物A和B分别避光搅拌,取料于PET模板上利用线棒涂膜,在90℃下干燥5min除去溶剂,形成膜厚度约2μm的涂膜。将形成有涂膜的基板冷却至室温,附上掩膜板,用高压汞灯1PCS光源,通过FWHM滤光片实现长波长辐射。通过掩膜板的缝隙在370~420nm波长的紫外线对涂膜进行曝光,随后于25℃下在2.5%的碳酸钠溶液中浸渍20s显影,再用超纯水洗,风干,在220℃下硬烘烤30min使图形定影,对得到的图形进行评价。
3.光固化组合物的性能评价
(1)储存稳定性
将液态的光固化组合物在室温下自然储存1个月后,根据以下标准在视觉上评价物质的沉淀程度:
A:没有观察到沉淀;
B:略微观察到沉淀;
C:观察到明显沉淀。
(2)感光度
曝光时,将在曝光步骤中光辐照区域显影后残膜率在90%或以上的最小曝光量评价为曝光需求量,曝光需求量越小表示灵敏度越高。
(3)显影性和图案完整性
用扫描电子显微镜(SEM)观察基板图案,以评价显影性和图案完整性。
显影性根据以下标准评价:
○:在未曝光部分未观察到残留物;
◎:在未曝光部分观察到少量残留物,但残留物可以接受;
●:在未曝光部分观察到明显残留物。
图案完整性根据以下标准评价:
◇:没有观察到图案缺陷;
□:观察到小部分图案有些许缺陷;
◆:明显观察到许多图案缺陷。
(4)热稳定性
用测厚仪测试硬烘烤前后膜厚度的变化,以评价材料的热稳定性。
评价结果如表2和表3中所示:
表2光固化组合物A
表3光固化组合物B
表2和表3中,PBG-304表示CN101508744A中公开的光引发剂1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基丙酮)-1-肟-乙酸酯,OXE-01表示1-(4-苯硫基-苯基)-辛-1,2-二酮-2-肟-O-苯甲酸酯,OXE-02表示1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-乙酮)-1-肟-乙酸酯,Irgacure907表示2-甲基-1-(4-甲硫基苯基)-2-吗啉基-丙烷-1-酮。
由表2和表3的结果可以看出,包含本发明通式(I)所示的双肟酯类光引发剂的光固化组合物具有很好的储存稳定性,在无色体系和颜料体系中均表现出了极佳的感光度、显影性及图案完整性,并且具有明显优于现有光引发剂的热稳定性。相较而言,PBG-304、OXE-01、OXE-02及Irgacure907在储存稳定性、感光度、显影性、图案完整性和热稳定性方面存在显著差距。
综上所述,本发明公开的通式(Ⅰ)所示的双肟酯类光引发剂的应用性能优异,应用于光固化组合物可极大的提高光固化产品的性能。
Claims (9)
1.一种双肟酯类光引发剂,其具有如通式(I)所示结构:
其中,
R1为其中,*表示连接位,X为空、单键或C1-C5的亚烷基基团;Y为O、S或R5N-基团,其中R5为氢、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基;
R2、R3相互独立地表示为C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基,任选地,上述基团中的氢可以被选自卤素、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团取代;条件是,R2和R3中至少一个是未被取代或被一个或多个选自卤素、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团取代的环烷基烷基,所述环烷基烷基的结构为其中n为1-5的整数,m为1-6的整数;
R4表示为C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C3-C20的杂芳基、C6-C20的芳基,任选地,上述基团中的氢可以被选自卤素、苯基、硝基、羟基、羧基、磺酸基、氨基、氰基和烷氧基的基团所取代。
2.根据权利要求1所述的双肟酯类光引发剂,其特征在于:R1中,X为空、单键、亚甲基、亚乙基或亚丙基;Y为O、S或R5N-基团,其中R5为氢、C1-C10的直链或支链烷基。
4.根据权利要求1所述的双肟酯类光引发剂,其特征在于:R4表示为C1-C5的直链或支链烷基、C3-C8的环烷基、C4-C8的环烷基烷基、C4-C8的烷基环烷基、C3-C5的杂芳基、C6-C10的芳基,任选地,上述基团中的氢可以被选自卤素、硝基和烷氧基的基团所取代。
7.根据权利要求6所述的制备方法,其特征在于:所述Z选自F、Cl、Br或I。
8.根据权利要求6所述的制备方法,其特征在于:所述亚硝酸酯选自***、亚硝酸异戊酯或亚硝酸异辛酯,所述亚硝酸盐选自亚硝酸钠或亚硝酸钾。
9.权利要求1所述的双肟酯类光引发剂在光固化组合物中的应用。
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Denomination of invention: A Dioxime Ester Photoinitiator and Its Preparation Method and Application Granted publication date: 20160406 Pledgee: Zijin Trust Co.,Ltd. Pledgor: Changzhou Tronly New Electronic Materials Co.,Ltd. Registration number: Y2024980002889 |