CN108117616A - 二丁基芴基衍生物与其作为光引发剂的应用 - Google Patents
二丁基芴基衍生物与其作为光引发剂的应用 Download PDFInfo
- Publication number
- CN108117616A CN108117616A CN201711175135.1A CN201711175135A CN108117616A CN 108117616 A CN108117616 A CN 108117616A CN 201711175135 A CN201711175135 A CN 201711175135A CN 108117616 A CN108117616 A CN 108117616A
- Authority
- CN
- China
- Prior art keywords
- photocurable composition
- composition
- compound
- photoinitiator
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 19
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- -1 platedresist Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 239000002966 varnish Substances 0.000 claims description 7
- 238000001723 curing Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- DPPFREDTHDJUOI-UHFFFAOYSA-N 9,9-dibutylfluorene Chemical class C1=CC=C2C(CCCC)(CCCC)C3=CC=CC=C3C2=C1 DPPFREDTHDJUOI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000002775 capsule Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 238000013500 data storage Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000004377 microelectronic Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 238000010186 staining Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 235000013305 food Nutrition 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 0 *CC(c(cc1)cc2c1*(C=CCC1)=C1C2(*)*)=O Chemical compound *CC(c(cc1)cc2c1*(C=CCC1)=C1C2(*)*)=O 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BLPGWZAQVVZJOA-UHFFFAOYSA-N 1-butyl-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(CCCC)=CC=C2 BLPGWZAQVVZJOA-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WGVWLLANYKHNKL-UHFFFAOYSA-N 2-(9,9-dibutylfluoren-1-yl)-2-methyloxirane Chemical compound C(CCC)C1(C2=CC=CC=C2C=2C=CC=C(C1=2)C1(CO1)C)CCCC WGVWLLANYKHNKL-UHFFFAOYSA-N 0.000 description 2
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000007445 Chromatographic isolation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 238000011097 chromatography purification Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000003988 headspace gas chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZHQNDEHZACHHTA-UHFFFAOYSA-N CC1(C)c2ccccc2-c2c1cccc2 Chemical compound CC1(C)c2ccccc2-c2c1cccc2 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- VGEMYWDUTPQWBN-UHFFFAOYSA-N CCNCCOC Chemical compound CCNCCOC VGEMYWDUTPQWBN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic 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
- C08F222/00—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
- C08F222/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
- C08F222/00—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
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明提供了一种二丁基芴基衍生物和其作为光引发剂的应用以及其制备方法。本发明提供了含有所述化合物的光固化组合物和使用该组合物的光固化方法。
Description
技术领域
本发明涉及辐射光照射固化领域。具体的,本发明提供了新的二丁基芴基衍生物:2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮和其制备方法,以及2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮作为光引发剂的应用。
背景技术
辐射固化技术是指利用紫外光(UV)和电子束(EB)、红外光、可见光、激光、化学荧光等辐射光照射固化聚合物的新型技术,具有高效、经济、节能、环境友好的特点,属于新型节能环保技术。
光引发剂在国内涂料、油墨行业被广泛应用。随着人们生活水平的提高,对环境和食品安全问题越来越重视。包装业,尤其是食品和化妆品包装行业的彩色印刷,对有害挥发性有机物(VOC),如苯、四氯化碳、氯仿等的限量越来越严格。例如食品包装的印刷就严格规定了苯释放量最高限制为3mg/m2,烟草包装用品为0.01mg/m2。美欧国家的相关标准更加严格。我国是工业制造大国,包装行业产品对美欧国家的出口量越来越多,包装产物有害挥发性有机物的检出限量必须满足美欧国家的标准。
现在常用的光引发剂,如二苯甲酮、二苯乙二酮等,由于在使用过程中受光引发作用,会产生挥发性有机物,目前已经不能满足在食品和化妆品包装领域的检测标准要求。现有的某些咔唑和二苯并呋喃类化合物类的光引发剂,在储存、使用时,稳定性较差,同时由于所使用的原材料例如咔唑和二苯并呋喃的成本较高,所以导致光引发剂***高,而性能上没有特别优势。
现有技术中的光引发剂还存在光引发效率低,特别是对引发光源的波长要求具有一定限制,在某些波长范围内光引发效率低的缺陷。
因此,在光聚合技术领域中,还需要对环境更为友好,具有更高活性、容易制备且容易处理等优点的光引发剂和光固化方法。
发明内容
本发明提供了一种作为光引发剂的新的化合物。本发明还提供了一种含有所述新的化合物的光固化组合物,并提供了采用所述新化合物和光固化组合物的固化方法。本发明提供的化合物、固化组合物和光固化方法能够更有效地在波长范围内引发光聚合反应,而且本发明提供的化合物具有更高稳定性,以及易于制备和处理,对环境更为友好的特点。
具体的,本发明提供了一种光固化组合物,其包含:
(a)具有下式的光引发剂化合物
(b)可光聚合的碳碳双键式不饱和化合物。
在本发明的其中一个方面,本发明的光固化组合物中所述光引发剂化合物占该组合物重量的0.5-10%,优选为约3%。
本发明的光固化组合物中组分(b)的所述可光聚合的碳碳双键式不饱和化合物包括具有一个或多个烯双键的化合物。可光聚合的化合物单体的例子包括:丙烯酸烷基酯、甲基丙烯酸烷基酯、羟烷基酯、环氧烷基酯、(甲基)丙烯酰胺、N-取代的(甲基)丙烯酰胺、不饱和羧酸酐、不饱和酯、乙烯基醚、异氰脲酸酯、N-乙烯基杂环化合物等。
在本发明的一个方面,所述烯属不饱和可光聚合的化合物为烯属不饱和羧酸与多元醇或聚环氧化物的酯。所述不饱和羧酸的例子为丙烯酸、甲基丙烯酸、不饱和脂肪酸如亚麻酸或油酸。优选的,所述不饱和羧酸为丙烯酸和甲基丙烯酸。所述多元醇可为芳族,脂族或环脂族多元醇。芳族多元醇的例子为对苯二酚、4,4-二羟基联苯、2,2-二(4-羟基苯基)丙烷、以及线型酚醛树脂和酚醛树脂A。在本发明的另一个方面,所述烯属不饱和可光聚合的化合物为丙烯酸酯化的环氧树脂、丙烯酸烷基酯、丙烯酸烷氧基酯或其混合物,最优选为环氧丙烯酸酯、三羟甲基丙烷三丙烯酸酯或其混合物。
组分(b)中所述烯属不饱和可光聚合的化合物可以是其中的一种,也可以是其中的两种的混合物或是两种以上的混合物。
在本发明的可光聚合的组合物中,组分(b)烯属不饱和可光聚合的化合物一般用量为约10%至约70%,优选为约25%至约60%。
本发明提供的可光聚合的组合物中还可含有其它添加剂。例如防止过早聚合的热抑制剂、光稳定剂(如紫外线吸收剂)等。可使用的光稳定剂例如羟基苯基苯并***、羟基苯基-二苯甲酮等。
在本发明的其中又一个方面,本发明的光固化组合物中还含有反应性胺助引发剂,例如为水溶性叔胺类。所述胺助引发剂占该组合物重量的0.5-10%,优选为约7%。
在本发明的其中又一个方面,本发明的光固化组合物包含:
其中所述百分比为其在组合物中所占重量比。
本发明提供了上述本发明的光固化组合物的固化方法,包括将所述光固化组合物涂布在基材上,用波长在150-600nm的光进行照射。在本发明的其中一个方面,本发明的光固化组合物适合在波长在320-420nm,优选在340-400nm的范围内光照射进行固化。可用于本发明方面的固化方法的光源或辐射的例子包括发射波段在UV-可见光区之间的汞蒸气灯或者激光灯。
本发明提供了上述本发明的光固化组合物的应用,用于制造着色和非着色的油漆和清漆、粉末涂料、印刷油墨、印刷板、粘合剂、牙科组合物、凝胶涂料、电子学用光致抗蚀剂、电镀抗蚀剂、液体膜和干膜、阻焊剂、显示应用的滤色片用的抗蚀剂、在等离子体显示板、电致发光显示器和LCD的制造过程中产生结构用的抗蚀剂、LCD间隔物、用于全息数据存储、作为包封电气和电子元件的组合物、用于制造磁记录材料、微机械部件、光学开关、电镀掩模、蚀刻掩模、色彩打样体系、玻璃纤维电缆涂料、丝网印刷模版、用于通过立体平版印刷技术产生三维物体、用作图像记录材料、用于全息记录、微电子电路、脱色材料、用于使用微胶囊的图像记录材料。
本发明还提供了至少一个表面上涂有上述本发明的光固化组合物的涂布基材。
在本发明的其中一个方面,提供了具有下式的光引发剂化合物
在本发明的其中一个方面,提供了制备下式化合物的方法,
所述方法包括以下步骤:
在本发明的其中一个方面,其中步骤(5)包括:将2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉混合,搅拌回流反应约20小时,减压蒸馏出多余的吗啉,加入甲醇溶解剩余物,加热溶解后,静置、冷却。本发明的制备所述化合物的方法具有产率高、节省原料和降低成本的特点。
本发明的光引发剂化合物和包含所述光引发剂化合物的光固化组合的优点包括:
1.所述光引发剂化合物分子的光吸收波长较长,引发使用的灯光波长也较长,与其它光引发剂需要的波长短、能量高的要求比较,降低了对光能量的要求,可用光源范围更广,光利用效率更高,使用更方便。
2.所述光引发剂化合物分子的分子结构使其在有机溶剂的溶解度更高,方便实际应用。
3.所述光引发剂化合物分子相对具有其它杂原子的光引发剂的稳定性较高,同时由于本发明的化合物的制备方法使用的原材料成本较具有其它杂原子的光引发剂的低,因此具有***格和性能上的比较优势。
具体实施方式
通过下述实施例有助于进一步理解本发明,但不用于限制本发明的内容。
实施例1 2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮的合成
2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮的合成路径如下所示:
步骤(1)9,9-二丁基芴的合成:
于100mL三颈烧瓶中分别加入12mmol(1.99克)芴、0.5mmol(0.16克)相转移催化剂四正丁基溴化铵、4.5mL 50%的氢氧化钠水溶液,29mmol(3.1mL)正溴丁烷和50mL丁酮。加热回流3-4小时,并以薄层层析跟踪反应,直至反应结束。蒸馏除去溶剂丁酮后,用二氯甲烷萃取(10mL x 3次)。合并有机层,用无水硫酸钠干燥,旋转蒸发除去溶剂后得到目标产物。
步骤(2)2-(2-甲基丙酰基)-9,9-二丁基芴的合成:
于250mL三颈烧瓶中分别加入0.01mol(1.0mL)异丁酰氯、0.01mol(2.78克)9,9-二丁基芴和40mL二氯甲烷。磁力搅拌混合均匀,并以冰浴冷却。磁力搅拌下,于10℃以下分二次加入总计为0.012mol(1.58克)的三氯化铝,后升温至室温搅拌3小时,再升温至40℃继续搅拌1小时。搅拌下把反应混合物慢慢倒入100克冰水中。静置分层后,分离除去水层,有机层用冰水洗涤(30mL x 3次),基本呈中性。干燥后除去二氯甲烷得到目标产物。
步骤(3)2-(2-溴-2-甲基丙酰基)-9,9-二丁基芴的合成:
往250mL的三口烧瓶中加入二氯甲烷50mL,15mL 80%的硫酸,0.20mol的双氧水和0.10mol(34.85克)的2-(2-甲基丙酰基)-9,9-二丁基芴。温度控制在25-30℃,1.0-1.5小时内滴加0.07mol(3.6mL)溴素。滴加完毕溴素20分钟后HPLC检测2-(2-甲基丙酰基)-9,9-二丁基芴反应完全。冷却下,搅拌滴加30%的氢氧化钠溶液,中和上述反应混合物值pH为中性。静置、分层。水层用二氯甲烷萃取(20mL x 2次)。合并有机层,干燥、旋转蒸馏除去溶剂二氯甲烷,得到目标产物。
步骤(4)2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷的合成:
在250mL的三口烧瓶中加入50mL无水甲醇和0.12mol(2.76克)金属钠,制备出甲醇钠的甲醇溶液。温度控制在25-30℃,1.5-2.0小时内分三批加入0.10mol(4.27克)2-(2-溴-2-甲基丙酰基)-9,9-二丁基芴。加入完毕后,继续反应1小时。HPLC检测2-(2-溴-2-甲基丙酰基)-9,9-二丁基芴反应完全后,60℃旋转蒸馏除去溶剂甲醇,冷却得到白色固体。产物不经纯化,直接进行下步反应。
步骤(5)2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮的合成:
方法1:取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷3.67g(10.0mmol)加入100mL反应瓶中,加入吗啉2.61g(30.0mmol),于120-130oC搅拌反应20小时。点板跟踪反应结束后减压蒸馏出多余的吗啉等溶剂后,以石油醚-乙酸乙酯为流动相柱层析分离纯化得到目标化合物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮3.63g,产率83.7%。1H NMR(400MHz,CDCl3)δ:8.74(d,J=0.8Hz,1H),8.48(dd,J1=8.0Hz,J2=0.8Hz,1H),7.78-7.73(m,2H),7.39-7.37(m,3H),3.74(t,J=4.8Hz,4H),2.66-2.64(m,4H),2.05-2.00(m,4H),1.59(s,6H),1.13-1.06(m,4H),0.69-0.60(m,10H);13CNMR(100MHz,CDCl3)δ:202.9,151.9,149.8,145.2,140.0,129.6,128.1,127.0,125.0,123.0,120.6,119.0,76.9,67.4,55.0,47.1,40.1,26.0,23.0,20.4,13.8.ESRMs m/z=434.3[M+H]+。
根据核磁共振谱(氢谱、碳谱)和质谱结果确定为目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮。
方法2.取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷7.33g(20.0mmol)加入100mL反应瓶中,加入吗啉4.35g(50.0mmol),搅拌回流反应20小时。点板跟踪反应结束后减压蒸馏出多余的吗啉后,加入甲醇溶解剩余物,加热使其完全溶解后,静置、冷却,得到目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮7.14g,产率82.3%。
根据核磁共振谱(氢谱、碳谱)和质谱结果与合成方法1相同,即为目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮。
方法3.取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷7.33g(20.0mmol)加入100mL反应瓶中,加入吗啉1.74g(20.0mmol),N,N-二甲基甲酰胺10mL,搅拌回流反应20小时。后处理同合成方法2,得到目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮5.04g,产率58.1%。
方法4.取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷7.33g(20.0mmol)加入100mL反应瓶中,加入吗啉1.74g(100.0mmol),搅拌回流反应20小时。后处理同合成方法2,得到目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮7.32g,产率84.4%。
其中,方法1的产物收率(83.7%)稍高于方法2的产物收率(82.3%)。方法2不需要柱层析分离纯化产物,更适宜工业化生产。
方法3中,反应原料2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉的摩尔比为1:1时,产率低,只有58.1%;同时也由于2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷常温下为固体,二个反应原料相互溶解充分性稍差。
方法4中,反应原料2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉的摩尔比为1:5时,产物收率(84.4%)与合成方法2的收率(82.3%)没有明显提升,但是吗啉的摩尔比用量由2.5提升到5.0,吗啉的用量明显增加。
实施例2光固化清漆制剂的制备
根据以下配方配置光固化清漆制剂。
具体配方如下:
根据上述配方,以2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮作为光引发剂制备得到发明制剂。
通过制备只有光引发剂含量不同,其它配方组成都一样的光固化清漆制剂来制备和测试其它光引发剂制备得到的对比制剂。
包括:
以2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮作为光引发剂制备得到对比制剂1;
以2-甲基-1-(4-联苯基)-2-吗啉基-1-丙酮作为光引发剂制备得到对比制剂2。
实施例3固化效果测试
将实施例2中配制所得的清漆制剂用印刷适性仪涂布约15微米厚度于空白纸张上,用功率为50W/CM线功率的带可调过滤器的紫外灯,在360-420波长范围下,以100米/分速度进行固化,记录获得良好的表面及彻底固化所需要的灯下通过次数。结果如下表1所示。
表1紫外线照射固化效果测定结果
实施例4VOC释放分析
采用顶空-气相色谱法测定实施例3中用本发明的光引发剂制备的固化膜中的VOC释放量。
结果如下表2所示。
表2顶空-气相色谱法测定涂层固化层有害VOC的释放量测定结果
实施例5溶解度、黄变和气味分析
将固态光引发剂(本发明化合物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮;对比光引发剂2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮和2-甲基-1-(4-联苯基)-2-吗啉基-1-丙酮溶入液体聚合单体(1,6-己二醇二丙烯酸酯(HDDA)或二缩三丙二醇二丙烯酸酯(TPGDA))中,加热至50~60℃并混合均匀。溶解后的液体应在室温下贮存。测量其溶解度。观察黄变程度和人工评估气味。结果如下表3。
表3溶解度黄变和气味分析测定结果
实施例6稳定性分析
将实施例2配制所得的清漆制剂用15微米线棒涂布器施印到12×12cm纸板上,用一台功率为80瓦/厘米中压水银弧光灯以20米/分的速度进行固化。将纸板剪裁为10×10cm大小,完全浸入100ml蒸馏水、3%醋酸水溶液两种模拟液中,密封好在40℃条件下放置10天。取出印刷物,静置后直接进行HPLC分析模拟液中引发剂化合物含量。按600cm2印刷面积包装1kg食品计算,迁移率测量结果以g/Kg食品表示,其结果如表4所示。
表4稳定性分析结果
本发明出人意料地发现,创新性的化合物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮在光聚合反应中具有良好的性能,能够有效地在例如紫外(UV)光的照射时产生聚合引发基。而且本发明提供的光引发剂化合物和固化组合物的生产成本低,同时生产工艺简单,后处理简单,满足环境保护要求。本发明提供的光引发剂可以有效降低产品中各种VOC,包括苯或甲苯的释放量,适合应用于食品、烟草、化妆品等包装印刷行业。
Claims (10)
1.一种光固化组合物,其包含:
(a)具有下式的光引发剂化合物
(b)可光聚合的碳碳双键式不饱和化合物。
2.权利要求1的光固化组合物,其中所述光引发剂化合物占该组合物重量的0.5-10%,优选为约3%。
3.根据权利要求1的光固化组合物,其中所述碳碳双键式不饱和化合物为烯属不饱和羧酸与多元醇的酯或烯属不饱和羧酸与聚环氧化物的酯。
4.根据权利要求1-3中任一项的光固化组合物,其还含有反应性胺助引发剂,例如为水溶性叔胺类,所述胺助引发剂占该组合物重量的0.5-10%,优选为约7%。
5.根据权利要求1的光固化组合物,其包含:
其中所述百分比为其在组合物中所占重量比。
6.根据权利要求1-5中任何一项的光固化组合物的应用,用于制造着色和非着色的油漆和清漆、粉末涂料、印刷油墨、印刷板、粘合剂、牙科组合物、凝胶涂料、电子学用光致抗蚀剂、电镀抗蚀剂、液体膜和干膜、阻焊剂、显示应用的滤色片用的抗蚀剂、在等离子体显示板、电致发光显示器和LCD的制造过程中产生结构用的抗蚀剂、LCD间隔物、用于全息数据存储、作为包封电气和电子元件的组合物、用于制造磁记录材料、微机械部件、光学开关、电镀掩模、蚀刻掩模、色彩打样体系、玻璃纤维电缆涂料、丝网印刷模版、用于通过立体平版印刷技术产生三维物体、用作图像记录材料、用于全息记录、微电子电路、脱色材料、用于使用微胶囊的图像记录材料。
7.权利要求1-5中任何一项的光固化组合物的固化方法,包括将所述光固化组合物涂布在基材上,用波长在150-600nm范围的光进行照射,优选用波长在320-420nm范围的光进行照射。
8.一种具有下式的光引发剂化合物
9.一种制备下式化合物的方法,
包括以下步骤:
10.根据权利要求9的方法,其中步骤(5)包括:将2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉混合,搅拌回流反应约20小时,减压蒸馏出多余的吗啉,加入甲醇溶解剩余物,加热溶解后,静置、冷却。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711175135.1A CN108117616B (zh) | 2017-11-22 | 2017-11-22 | 二丁基芴基衍生物与其作为光引发剂的应用 |
US16/765,826 US11560362B2 (en) | 2017-11-22 | 2018-11-12 | Dibutylfluorene derivative and application thereof as photoinitiator |
PCT/CN2018/116999 WO2019101142A1 (zh) | 2017-11-22 | 2018-11-22 | 二丁基芴基衍生物与其作为光引发剂的应用 |
JP2020545844A JP7059384B2 (ja) | 2017-11-22 | 2018-11-22 | ジブチルフルオレニル誘導体及びその光開始剤としての使用 |
EP18881958.5A EP3715381B1 (en) | 2017-11-22 | 2018-11-22 | Dibutylfluorene derivative and application thereof as photoinitiator |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711175135.1A CN108117616B (zh) | 2017-11-22 | 2017-11-22 | 二丁基芴基衍生物与其作为光引发剂的应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108117616A true CN108117616A (zh) | 2018-06-05 |
CN108117616B CN108117616B (zh) | 2019-08-09 |
Family
ID=62227901
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711175135.1A Active CN108117616B (zh) | 2017-11-22 | 2017-11-22 | 二丁基芴基衍生物与其作为光引发剂的应用 |
Country Status (5)
Country | Link |
---|---|
US (1) | US11560362B2 (zh) |
EP (1) | EP3715381B1 (zh) |
JP (1) | JP7059384B2 (zh) |
CN (1) | CN108117616B (zh) |
WO (1) | WO2019101142A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019101142A1 (zh) * | 2017-11-22 | 2019-05-31 | 惠州市华泓新材料股份有限公司 | 二丁基芴基衍生物与其作为光引发剂的应用 |
WO2020241328A1 (ja) * | 2019-05-29 | 2020-12-03 | 株式会社Dnpファインケミカル | カラーフィルタ用感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 |
WO2022091711A1 (ja) * | 2020-10-27 | 2022-05-05 | 株式会社Dnpファインケミカル | 感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2021125132A1 (zh) * | 2019-12-20 | 2021-06-24 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106537254A (zh) * | 2014-07-15 | 2017-03-22 | 东京应化工业株式会社 | 感光性组合物及化合物 |
CN107793503A (zh) * | 2017-09-28 | 2018-03-13 | 大连天源基化学有限公司 | 一种紫外光引发剂及其合成方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7037953B2 (en) * | 2000-03-29 | 2006-05-02 | Sun Chemical Corporation | Radiation curable aqueous compositions |
US7105688B2 (en) * | 2003-08-25 | 2006-09-12 | Eastman Chemical Company | Ethylenically-unsaturated red anthraquinone dyes |
CN104661997B (zh) | 2012-05-03 | 2018-06-26 | 韩国化学研究院 | 新型芴类肟酯化合物,及含有该芴类肟酯化合物的光聚合引发剂和光阻剂组合物 |
CN102766045B (zh) | 2012-07-31 | 2014-03-05 | 惠州市华泓新材料有限公司 | 二苯甲酮衍生物与其作为光引发剂的应用 |
CN103012317B (zh) | 2012-12-23 | 2014-10-15 | 惠州市华泓新材料有限公司 | 烷基苯基衍生物和其作为光引发剂的应用 |
KR101435652B1 (ko) | 2014-01-17 | 2014-08-28 | 주식회사 삼양사 | 신규한 β-옥심에스테르 플루오렌 화합물, 이를 포함하는 광중합 개시제 및 포토레지스트 조성물 |
CN104004395B (zh) | 2014-06-17 | 2016-08-17 | 广东美涂士建材股份有限公司 | 一种木皮用uv辊涂弹性底涂涂料及其制备方法与实施工艺 |
CN107272336A (zh) | 2016-04-06 | 2017-10-20 | 常州强力先端电子材料有限公司 | 一种含芴类光引发剂的感光性树脂组合物及其应用 |
JP6641468B2 (ja) * | 2015-10-08 | 2020-02-05 | 常州強力電子新材料股▲分▼有限公司CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS Co., Ltd. | フルオレン含有オキシムエステル類光開始剤、その合成、それを含有する感光性樹脂組成物及びその使用 |
EP3392232B1 (en) * | 2015-12-15 | 2021-02-17 | Changzhou Tronly Advanced Electronic Materials Co., Ltd. | Fluorene multifunctional photoinitiator and preparation and use thereof, and photosensitive resin composition containing fluorene photoinitiator and use thereof |
CN106883114B (zh) | 2015-12-15 | 2019-11-19 | 常州强力先端电子材料有限公司 | 一种芴类多官能度光引发剂及其制备和应用 |
JP6633425B2 (ja) * | 2016-02-26 | 2020-01-22 | 東京応化工業株式会社 | 硬化性樹脂組成物 |
KR102347918B1 (ko) | 2016-03-28 | 2022-01-05 | 동우 화인켐 주식회사 | 착색 감광성 수지 조성물, 이를 이용하여 제조된 컬러필터 및 화상표시장치 |
CN106010144B (zh) | 2016-06-20 | 2019-04-23 | 上海飞凯光电材料股份有限公司 | 一种uv-led固化用光纤涂覆树脂及其制备方法和应用 |
EP3584242A4 (en) * | 2017-02-17 | 2020-12-23 | Changzhou Tronly Advanced Electronic Materials Co., Ltd. | FLUORENYLAMINOCETONE PHOTOINITIATOR, ITS PREPARATION PROCESS AND UV PHOTOSETTING COMPOSITION CONTAINING IT |
CN108117616B (zh) | 2017-11-22 | 2019-08-09 | 惠州市华泓新材料股份有限公司 | 二丁基芴基衍生物与其作为光引发剂的应用 |
-
2017
- 2017-11-22 CN CN201711175135.1A patent/CN108117616B/zh active Active
-
2018
- 2018-11-12 US US16/765,826 patent/US11560362B2/en active Active
- 2018-11-22 WO PCT/CN2018/116999 patent/WO2019101142A1/zh unknown
- 2018-11-22 JP JP2020545844A patent/JP7059384B2/ja active Active
- 2018-11-22 EP EP18881958.5A patent/EP3715381B1/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106537254A (zh) * | 2014-07-15 | 2017-03-22 | 东京应化工业株式会社 | 感光性组合物及化合物 |
CN107793503A (zh) * | 2017-09-28 | 2018-03-13 | 大连天源基化学有限公司 | 一种紫外光引发剂及其合成方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019101142A1 (zh) * | 2017-11-22 | 2019-05-31 | 惠州市华泓新材料股份有限公司 | 二丁基芴基衍生物与其作为光引发剂的应用 |
US11560362B2 (en) | 2017-11-22 | 2023-01-24 | Huizhou Huahong New Material Co., Ltd. | Dibutylfluorene derivative and application thereof as photoinitiator |
WO2020241328A1 (ja) * | 2019-05-29 | 2020-12-03 | 株式会社Dnpファインケミカル | カラーフィルタ用感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 |
JP6817503B1 (ja) * | 2019-05-29 | 2021-01-20 | 株式会社Dnpファインケミカル | カラーフィルタ用感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 |
WO2022091711A1 (ja) * | 2020-10-27 | 2022-05-05 | 株式会社Dnpファインケミカル | 感光性着色樹脂組成物、硬化物、カラーフィルタ、及び表示装置 |
Also Published As
Publication number | Publication date |
---|---|
US20200385359A1 (en) | 2020-12-10 |
EP3715381A1 (en) | 2020-09-30 |
EP3715381A4 (en) | 2020-09-30 |
CN108117616B (zh) | 2019-08-09 |
WO2019101142A1 (zh) | 2019-05-31 |
JP7059384B2 (ja) | 2022-04-25 |
US11560362B2 (en) | 2023-01-24 |
EP3715381B1 (en) | 2024-06-12 |
JP2021504555A (ja) | 2021-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108117616B (zh) | 二丁基芴基衍生物与其作为光引发剂的应用 | |
US4022674A (en) | Photopolymerizable compounds and compositions comprising the product of the reaction of a monomeric ester and a polycarboxy-substituted benzophenone | |
KR102362859B1 (ko) | 중합성 기를 함유하는 플루오렌 옥심 에스테르 광 개시제, 및 이의 제조방법 및 용도 | |
CN107344918B (zh) | 一类含二苯乙烯的肟酯类化合物及其制备方法和应用 | |
CN103012317B (zh) | 烷基苯基衍生物和其作为光引发剂的应用 | |
JP6000456B2 (ja) | インクにおける光開始剤および光増感剤としてのケトクマリン | |
CN112574110B (zh) | 酰基取代吡唑啉硫鎓盐衍生物的制备及其应用 | |
CN105152898B (zh) | 苯基丁酮衍生物与其作为光引发剂的应用 | |
CN109265582B (zh) | 低温液态胺基酮型光引发剂化合物及其混合物 | |
CN101434543B (zh) | 多官能二苯甲酮衍生物及其作为光引发剂的用途 | |
CN102766045B (zh) | 二苯甲酮衍生物与其作为光引发剂的应用 | |
CN103274978B (zh) | 一种三芳基硫鎓盐及其制备方法和应用 | |
CN110358353A (zh) | 一种紫外光固化光纤着色墨组合物及其应用 | |
JPH0794519B2 (ja) | 活性エネルギー線硬化性樹脂組成物並びに被覆組成物および印刷インキ組成物 | |
CN112939779B (zh) | 适用于uv-led深层光聚合的对苯二甲酰甲酸酯型光引发剂及其制备方法 | |
CN112574184B (zh) | 环氧化物取代的吡唑啉衍生物、光固化组合物以及制备方法 | |
CN108299213B (zh) | 一类二苯胺基联苯基羰基类化合物在光固化配方体系中的应用 | |
CN108503556B (zh) | 以联苯基二苯基胺为共轭主体结构的羰基类化合物及其制备方法与应用 | |
CN112707870A (zh) | 一种吩嗪衍生物类光引发剂及其制备方法和用途 | |
CN106565865B (zh) | 一种低voc释放光引发剂、其制备方法及应用 | |
CN114196226B (zh) | 一类香豆素染料、可用于超声固化的复合引发剂、其制备方法和应用 | |
WO2016000477A1 (zh) | (4-苯基苯甲酰基)苯甲酸酯及其作为光引发剂的用途 | |
CN113156766B (zh) | 一种感光树脂组合物及其应用 | |
CN115286641B (zh) | 一种硫杂蒽酮类单组分可见光引发剂及其制备方法和应用 | |
CN110105256B (zh) | α-胺基酮-二苯乙烯硫鎓盐类化合物及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |