CN107621752A - 一种混杂型光敏树脂及其制备方法 - Google Patents
一种混杂型光敏树脂及其制备方法 Download PDFInfo
- Publication number
- CN107621752A CN107621752A CN201610550205.6A CN201610550205A CN107621752A CN 107621752 A CN107621752 A CN 107621752A CN 201610550205 A CN201610550205 A CN 201610550205A CN 107621752 A CN107621752 A CN 107621752A
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- Prior art keywords
- photosensitive resin
- alkyl
- represented
- branched
- reaction
- Prior art date
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- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 9
- -1 (methyl) acryloxy functionality Chemical group 0.000 claims abstract description 16
- 238000000016 photochemical curing Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 125000003566 oxetanyl group Chemical group 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 2
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002642 lithium compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 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
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 37
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005764 inhibitory process Effects 0.000 abstract description 6
- 150000005839 radical cations Chemical class 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000002091 cationic group Chemical group 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UJMZZAZBRIPOHZ-UHFFFAOYSA-N 2-ethylhexan-1-ol;titanium Chemical compound [Ti].CCCCC(CC)CO UJMZZAZBRIPOHZ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- PSQWUOJNMMZDKW-UHFFFAOYSA-N 3-ethyl-3-(oxiran-2-ylmethoxymethyl)oxetane Chemical compound C1OC1COCC1(CC)COC1 PSQWUOJNMMZDKW-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)(CN)CO* Chemical compound CC(*)(CN)CO* 0.000 description 1
- CSHZUQSDZADLIZ-UHFFFAOYSA-N CC1(COC)CNC1 Chemical compound CC1(COC)CNC1 CSHZUQSDZADLIZ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 210000004905 finger nail Anatomy 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- 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
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F20/68—Esters
-
- 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
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/12—Esters of phenols or saturated alcohols
- C08F22/20—Esters containing oxygen in addition to the carboxy oxygen
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Abstract
本发明公开一种具有如通式(I)所示结构的混杂型光敏树脂,该光敏树脂含氧杂环丁烷官能团和(甲基)丙烯酰氧基官能团,功能性基团之间彼此呼应且官能度可调可控,非常适用于自由基‑阳离子光固化体系,固化速度快,不存在氧阻聚问题,且固化膜硬度高,柔韧性好,附着性和耐热性优异。
Description
技术领域
本发明属于有机化学领域,具体涉及一种混杂型光敏树脂及其制备方法。
背景技术
根据固化机理,辐射固化技术所用的引发体系主要有自由基型固化体系和阳离子型固化体系两种。自由基型固化体系固化速度快,引发剂种类多,对其研究较为深入,相关理论较为成熟,但也存在难以克服的缺陷,如:固化时体积收缩较大,严重影响涂层对基材的附着性;氧阻聚现象较严重,薄涂层表面固化困难;对于紫外光辐射不到的死角,完全不能固化,等等。阳离子型固化体系固化后体积收缩小,附着力强,且固化过程中不存在氧阻聚的问题,对于较深的部位或紫外光辐射不到的部位,可通过后固化有效的固化完全,缺点是固化速度慢,生产效率不高,且适用的引发剂种类较少。
近年来,针对自由基型引发体系和阳离子型引发体系的不同特点,出现了自由基-阳离子混合聚合体系,能够有效综合自由基固化和阳离子固化的优点,从而制得性能优良的固化产品。然而,适用于这类固化体系的预聚物种类不多,选择性有限,且体系中自由基光固化树脂和阳离子光固化树脂的固化速度很难达到同步固化,从而导致固化后的产品硬度及附着性不佳。
混杂型光敏树脂是克服此类缺陷的重要研究方向。目前已有一些关于混杂型光敏树脂的专利报道,例如,JP2011168561A公开了一种具有多个氧杂环丁烷官能团和丙烯酰氧基官能团的化合物,其具有较快的固化速度和较高的硬度,但是该类化合物柔韧性差,附着性不够好,很大程度上影响了感光材料的性能。
发明内容
针对现有技术的不足,本发明的目的在于提供一种应用性能好的混杂型光敏树脂及其制备方法。该光敏树脂含氧杂环丁烷官能团和(甲基)丙烯酰氧基官能团,且官能度可调可控,应用于自由基-阳离子固化体系时固化速度快,不存在氧阻聚问题,且固化膜硬度高,柔韧性好,附着性和耐热性佳。
为了实现上述目的,本发明的混杂型光敏树脂,具有如下通式(I)所示结构:
R1表示C1-C40的直链或支链的m价烷基、C2-C20的m价链烯基、C6-C40的m价芳基,其中的-CH2-可任选地(optionally)被氧原子、-NH-或者1,4-亚苯基所取代,条件是两个-O-不直接相连;并且任选地,这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;
R2表示C1-C20的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连,并且任选地,基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;
R3表示氢、卤素、硝基、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、C2-C10的链烯基、C6-C20的芳基,任选地,这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;
R表示氢或者甲基;
m表示1-8的整数。
在上述通式(I)所示结构中,m价连接基团R1将m个氧杂环丁烷官能团和m个(甲基)丙烯酰氧基官能团衔接成一个整体。
作为优选技术方案,R1表示C1-C40的直链或支链的m价烷基、C2-C10的直链或支链的m价链烯基、C6-C30的m价芳基,其中的-CH2-可任选地被氧原子、-NH-或者1,4-亚苯基所取代,条件是两个-O-不直接相连;且任选地,这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代。
示例性地,R1可选自下列结构:
C1-C12的直链或支链的1-4价烷基、CH3-O-CH2CH2*、 *CH2CH2-NH-CH2CH2*、
优选地,R2表示C1-C10的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连。
进一步优选地,R2表示C1-C6的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连。
优选地,R3表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的环烷基烷基、C4-C10的烷基环烷基、C2-C8的链烯基、苯基。进一步优选地,R3表示C1-C4的直链或支链烷基、或C4-C8的环烷基烷基。
m优选为1-6的整数,更优选1-4的整数。
本发明公开的内容中,除另有说明,相关术语具有本领域通常理解的含义。数值范围包括端点值和端点值之间的所有点值,例如″C1-C10″包括C1、C2、C3、C4、C5、C6、C7、C8、C9、C10,″1-4的整数″包括1、2、3、4。
相应地,本发明还涉及上述通式(I)所示混杂型光敏树脂的制备方法,该方法以通式(II)所示含羟基化合物和通式(III)所示含氧杂环丁烷基化合物为起始原料,包括以下步骤:
(1)开环反应
将通式(II)化合物和通式(III)化合物在催化剂存在条件下反应,得到中间体;其反应式如下:
(2)酯化/酯交换反应
中间体与(甲基)丙烯酸或(甲基)丙烯酸酯在催化剂存在条件下反应,得到产物;
其中,R4表示氢或C1-C4烷基(如CH3、CH3CH2、CH3CH2CH2等)。
步骤(1)反应中使用的催化剂可以是:碱金属氢氧化物,如氢氧化钠、氢氧化钾等;醇的碱金属盐,如甲醇钠、乙醇钾、叔丁醇钠等;碱金属碳酸盐,如碳酸钠、碳酸钾等;碱金属碳酸氢盐,如碳酸氢钠、碳酸氢钾等;烷基金属锂化合物,如丁基锂、苯基锂等;胺基锂化合物,如二异丙基氨基锂、六甲基二硅氨基锂等。催化剂的用量对本领域技术人员而言是容易确定的,优选地,催化剂用量为通式(II)化合物的摩尔量的0.1-20%,更优选1-20%。
根据原料种类,步骤(1)的反应体系可任选地包含有机溶剂。对适用的溶剂种类没有特别限定,只要能够溶解反应原料且不对反应产生负面影响即可,例如可以是:乙腈、丙腈、苄腈等腈类溶剂;N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等酰胺类溶剂;四氢呋喃、二氧杂环己烷等醚类溶剂;苯、甲苯、二甲苯等芳香族溶剂。这些溶剂可以单独一种使用,也可以是两种以上混合使用,总用量可根据反应体系的均一性和搅拌性进行适当调节,这对本领域技术人员而言是容易确定的。
步骤(1)的反应温度通常为25-200℃,优选50-150℃。对反应压力没有特别限制,一般情况下常压即可。反应结束后,调节pH至中性,过滤、水洗、萃取、减压蒸馏,得到中间体化合物。
步骤(2)中,中间体化合物与(甲基)丙烯酸进行酯化反应、或者与(甲基)丙烯酸酯进行酯交换反应,从而得到通式(I)化合物。
步骤(2)的反应在含有催化剂的有机溶剂中进行,对溶剂种类没有特别限定,只要能够溶解反应原料且不对反应产生负面影响即可,如苯、甲苯、二甲苯等芳香族溶剂。溶剂可以单独一种使用,也可以是两种以上混合使用,总用量可根据反应体系的均一性和搅拌性进行适当调节,这对本领域技术人员而言是容易确定的。
酯化反应中使用的催化剂可以是无机酸,如:盐酸、磷酸、硼酸、浓硫酸等,也可以是有机酸,如:对甲苯磺酸、甲磺酸等。酯交换反应中使用的催化剂可以是钛酸酯类化合物,如钛酸-2-乙基己酯、钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四异丁酯等中的一种或两种以上的组合。催化剂的用量对本领域技术人员而言是容易确定的,优选地,催化剂用量为中间体化合物的0.05-5wt%,更优选0.1-2wt%。
反应温度通常为0-200℃,优选50-150℃。反应结束后,水洗至中性,减压蒸馏除去溶剂,得到目标化合物。
本发明的混杂型光敏树脂包含多个氧杂环丁烷官能团和(甲基)丙烯酰氧基官能团。通过结构优化,功能性基团之间彼此呼应,导致该树脂非常适用于自由基-阳离子光固化体系,固化速度快,不存在氧阻聚问题,且固化膜硬度高,柔韧性好,附着性和耐热性优异。
具体实施方式
以下将结合实施例对本发明作进一步具体说明,但是本发明的范围不局限于这些实施例。
制备实施例
实施例1
(1)中间体1a的制备:
向装有搅拌装置、温度计、回流冷凝管的250ml四口烧瓶中加入23g乙醇和2g氢氧化钠,搅拌升温至50℃,滴加86g 3-乙基-3-[(环氧乙烷基甲氧基)甲基]氧杂环丁烷,1h滴加完,继续搅拌反应,气相跟踪至乙醇含量不再变化,停止加热,调节pH至中性,过滤,水洗,萃取,减压蒸馏得到103g中间体1a。
(2)化合物1的制备:
向装有回流冷凝管的250ml四口烧瓶中加入100g中间体1a、33g丙烯酸、0.2g对甲苯磺酸及100ml甲苯,加热回流反应跟踪至不再有水带出,停止反应。降温,水洗至中性,减压蒸馏除去溶剂,得到目标产物120g。
化合物1的结构通过GC-MS和1H-NMR得到确认。
MS(m/e):272(M)
1H-NMR(CDCl3,500MHz):δ0.96(3H,m),δ1.13(2H,m),δ1.25(2H,m),δ3.29(2H,s),δ3.42(2H,m),δ3.61(4H,d),δ4.61(1H,m),δ4.66(4H,s),δ5.82-6.42(3H,m)。
实施例2
(1)中间体2a的制备:
向装有搅拌装置、温度计、回流冷凝管的1000ml四口烧瓶中加入265g原料1、4g氢氧化钠及300ml甲苯,搅拌升温至80℃,滴加258g 3-乙基-3-[(环氧乙烷基甲氧基)甲基]氧杂环丁烷,1.5h滴加完,继续搅拌反应,气相跟踪至原料1含量不再变化,停止加热,调节pH至中性,过滤,水洗、萃取,减压蒸馏得到507g中间体2a。
(2)化合物2的制备:
向装有回流冷凝管的四口烧瓶中加入100g中间体2a、24.7g甲基丙烯酸、0.2g对甲苯磺酸及130ml甲苯,加热回流反应至不再有水带出,停止反应。降温,水洗至中性,减压蒸馏除去溶剂,得到目标化合物116g。
化合物2的结构通过GPC和IR得到确认。
GPC:
IR(KBr),ν/cm-1:981(s,),1630(s,C=C),1200(m,C-O-C),1720(s,C=O)。
实施例3
参照实施例1和2的方法,由相应试剂合成具有表1中所示结构的化合物3-11:
表1
性能测试
1、固化性能测试
以上述实施例的化合物为例,配以光引发剂,对本发明所述光敏树脂的固化性能进行测试。
测试过程中,以具有相同官能度的纯阳离子体系或纯自由基体系作为比较对象,包括:单官能度阳离子单体苯基缩水甘油醚(960,湖北巨胜科技有限公司)、双官能度阳离子单体双酚A型环氧树脂(E51,江苏三木集团)、三官能度阳离子单体4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯(TDE-85,天津津东化工厂);单官能度自由基单体丙烯酸-β-羟乙酯(HEA,沙多玛)、双官能度自由基单体1,6-己二醇二丙烯酸酯(HDDA,沙多玛)、三官能度自由基单体三羟甲基丙烷三丙烯酸酯(TMPTA,沙多玛)。
测试中,使用的阳离子引发剂为PAG-202,自由基引发剂为184,其结构如下:
(1)测试1—阳离子单体
参照表2所示配方选取原料,在暗室中搅拌均匀后,取样于PET膜,25#线棒涂布,形成膜厚约25μm的涂膜。将涂有涂层的PET膜置于履带式曝光机(RW-UV.70201,波长300-500nm)中进行曝光,曝光单次所接受的能量为80mj/cm2,记录各组配方固化完全所需的最低能量。
参照漆膜干燥时间测试标准GB/T 1728-1979中指触法来评价表面固化速度,即用手指轻触涂层,以表面滑爽,不粘手表示表面固化完全;采用指抠法测量底部固化速度,即用指甲轻抠涂层,以无脱落,无露底现象表示底层固化完全。
对本发明化合物与具有相应阳离子官能度的单体的固化性能进行测试。
表2
(2)测试2—自由基单体
依据表3所示配方,并参照测试1所示方法,对本发明化合物与具有相应自由基官能度的单体的固化性能进行测试。
表3
从表2-3的结果可以看到,本发明的混杂型光敏树脂在配以自由基-阳离子光引发剂时,在固化效率方面具有明显优势,固化完全所需的能量明显低于具有相同阳离子或自由基官能度的单体,不存在氧阻聚问题。在同等官能度情况下,本发明的光敏树脂具有普遍更优的固化速度。
2、固化成膜后性能测试
通过应用于示例性光固化组合物,对本发明的混杂型光敏树脂固化成膜后的性能进行评价,主要包括膜硬度、附着性、柔韧性和耐热性(以玻璃化转变温度衡量)。其中,
本发明的光固化组合物按如下比例进行制备:
本发明的光敏树脂 98质量份
阳离子引发剂PAG-202 1质量份
自由基引发剂184 1质量份;
对比例1的光固化组合物按如下比例进行制备:
阳离子聚合单体E-51 98质量份
阳离子引发剂PAG-202 2质量份;
对比例2的光固化组合物按如下比例进行制备:
自由基聚合单体TMPTA 98质量份
自由基引发剂184 2质量份;
对比例3的光固化组合物按如下比例进行制备:
光固化聚合单体即化合物A 98质量份
阳离子引发剂PAG-202 1质量份
自由基引发剂184 1质量份
其中,化合物A是JP2011168561A中公开的化合物,结构如下:
将配方组合物于暗室中搅拌均匀,以25#线棒分别涂布在玻璃基板上,获得厚度约为25μm的涂层,然后置于履带式曝光机(RW-UV.70201,波长300-500nm)中充分曝光10次,单次曝光为80mj/cm2,然后放置24h后进行测试。
(1)铅笔硬度测试
在温度23℃,相对湿度50%的条件下对本发明和对比例的固化膜进行测试。以GB/T 6739-2006中规定的铅笔硬度评价方法为标准,将铅笔插入试验仪器中并用夹子将其固定,保持水平,铅笔的尖端放在漆膜表面上,以1mm/s的速度朝离开自己的方向推动至少7mm距离,如果未出现划痕,在未测试区域重复实验,更换较高硬度的铅笔直至出现至少3mm长的划痕为止,以没有使涂层出现划痕的最硬的铅笔的硬度表示涂层的硬度。
(2)附着性测试
在温度23℃,相对湿度50%的条件下对本发明和对比例的固化膜进行测试。以GB/T 9286-1998中规定的漆膜划格评价方法为标准,将涂膜切割为百格,刀尖在切割时要划及底材,并且刀尖要锋利,刀尖与涂膜成45度角。用软毛刷刷去漆屑,将3M透明胶带粘在划好的百格上,并施力使胶带牢固的粘在涂膜面及划格部位。在2min内,拿住3M胶带的一端,并呈60度角度,在1秒内平稳地撕离胶带,并按下述标准进行评价。
0级:切割边缘完全平滑无一脱落;
1级:在切口交叉处有少许涂层脱落,但交叉切割面积受影响不能明显大于5%;
2级:在切口交叉处和/或沿切口边缘有涂层脱落,受影响明显大于5%,但不能明显大于15%;
3级:涂层沿切割边缘部分或全部以大碎片脱落,和/或在格子不同部位上部分或全部剥落,受影响的交叉切割面积明显大于15%,但不能明显大于35%;
4级:涂层沿切割边缘大碎片剥落,和/或一些方格部分或全部脱落,受影响的交叉切割面积明显大于35%,但不能明显大于65%;
5级:剥落的程度超过4级。
(3)柔韧性
在温度23℃,相对湿度70%的条件下对实施例和对比例的固化膜进行测试,以GB/T1731-93漆膜柔韧性测试方法为依据,将涂有固化涂层的马口铁板的外侧沿长度方向依次卷绕在10、5、4、3、2、1毫米的棒轴上,弯曲2-3s,用放大镜观察,以涂料层破坏的最小的棒轴的直径来表示光固化涂层的柔韧性。
(4)耐热性测试
利用差示扫描量热仪(PE DSC8000)测试本发明和对比例得到的固化膜的玻璃化转变温度,测试条件:氮气氛围,以10℃/min的速率从-20℃加热至200℃,在200℃保持1min,然后以10℃/min的速率从200℃冷却至-20℃,在-20℃保持1min,接着在以10℃/min的速率从-20℃加热至200℃,从而测得玻璃化转变温度Tg(℃)。
测试和评价结果汇总于表4中。
表4
从表4可以看到,本发明的混杂型光敏树脂应用于自由基-阳离子固化体系,相比于E51和TMPTA,能够赋予固化膜明显更高的硬度、更佳的附着性、柔韧性和更好的耐热性;并且相比于同类化合物A,在这四个方面也表现出了更好的应用性能。
综上所述,本发明提供的新型混杂型光敏树脂化合物综合了阳离子固化和自由基固化的优点,固化效率高,固化膜硬度、附着性、柔韧性和耐热性优异,且合成方法简单,品种多,对光固化领域的推广应用有很好的推动作用。
Claims (10)
1.一种混杂型光敏树脂,具有如下通式(I)所示结构:
R1表示C1-C40的直链或支链的m价烷基、C2-C20的m价链烯基、C6-C40的m价芳基,其中的-CH2-可任选地(optionally)被氧原子、-NH-或者1,4-亚苯基所取代,条件是两个-O-不直接相连;并且任选地,这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;
R2表示C1-C20的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连,并且任选地,基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;
R3表示氢、卤素、硝基、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、C2-C10的链烯基、C6-C20的芳基,任选地,这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代;
R表示氢或者甲基;
m表示1-8的整数。
2.根据权利要求1所述的混杂型光敏树脂,其特征在于:R1表示C1-C40的直链或支链的m价烷基、C2-C10的直链或支链的m价链烯基、C6-C30的m价芳基,其中的-CH2-可任选地被氧原子、-NH-或者1,4-亚苯基所取代,条件是两个-O-不直接相连;且任选地,这些基团中的一个或多个氢原子可以各自独立地被选自烷基、卤素、硝基的基团所取代。
3.根据权利要求1或2所述的混杂型光敏树脂,其特征在于,R1选自下列结构:
C1-C12的直链或支链的1-4价烷基、CH3-O-CH2CH2*、 *CH2CH2-NH-CH2CH2*、
4.根据权利要求1所述的混杂型光敏树脂,其特征在于:R2表示C1-C10的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连;优选地,R2表示C1-C6的直链或支链亚烷基,其主链中的-CH2-可任选地被氧原子取代,条件是两个-O-不直接相连。
5.根据权利要求1所述的混杂型光敏树脂,其特征在于:R3表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的环烷基烷基、C4-C10的烷基环烷基、C2-C8的链烯基、苯基;优选地,R3表示C1-C4的直链或支链烷基、或C4-C8的环烷基烷基。
6.根据权利要求1所述的混杂型光敏树脂,其特征在于:m为1-6的整数,优选1-4的整数。
7.权利要求1-6中任一项所述的混杂型光敏树脂的制备方法,以通式(II)所示含羟基化合物和通式(III)所示含氧杂环丁烷基化合物为起始原料,包括以下步骤:
(1)开环反应
将通式(II)化合物和通式(III)化合物在催化剂存在条件下反应,得到中间体;其反应式如下:
(2)酯化/酯交换反应
中间体与(甲基)丙烯酸或(甲基)丙烯酸酯在催化剂存在条件下反应,得到产物;
其中,R4表示氢或C1-C4烷基。
8.根据权利要求7所述的制备方法,其特征在于:步骤(1)反应中使用的催化剂选自碱金属氢氧化物、醇的碱金属盐、碱金属碳酸盐、碱金属碳酸氢盐、烷基金属锂化合物、和胺基锂化合物中的一种或两种以上的组合。
9.根据权利要求7所述的制备方法,其特征在于:步骤(2)中,中间体化合物与(甲基)丙烯酸进行酯化反应、或者与(甲基)丙烯酸酯进行酯交换反应,从而得到产物;酯化反应中使用的催化剂是无机酸或有机酸,酯交换反应中使用的催化剂是钛酸酯类化合物。
10.权利要求1-6中任一项所述的混杂型光敏树脂在自由基-阳离子光固化体系中的应用。
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JP2019522002A (ja) | 2019-08-08 |
CN107621752B (zh) | 2019-11-12 |
JP6680910B2 (ja) | 2020-04-15 |
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EP3486724A1 (en) | 2019-05-22 |
US20190391491A1 (en) | 2019-12-26 |
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US10642155B2 (en) | 2020-05-05 |
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