KR102125820B1 - Photopolymerization initiator comprising oxime compounds and photocurable electroductive ink composition having the same - Google Patents
Photopolymerization initiator comprising oxime compounds and photocurable electroductive ink composition having the same Download PDFInfo
- Publication number
- KR102125820B1 KR102125820B1 KR1020180168371A KR20180168371A KR102125820B1 KR 102125820 B1 KR102125820 B1 KR 102125820B1 KR 1020180168371 A KR1020180168371 A KR 1020180168371A KR 20180168371 A KR20180168371 A KR 20180168371A KR 102125820 B1 KR102125820 B1 KR 102125820B1
- Authority
- KR
- South Korea
- Prior art keywords
- unsubstituted
- substituted
- straight chain
- branched
- photopolymerization initiator
- Prior art date
Links
- -1 oxime compounds Chemical class 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000003999 initiator Substances 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000002270 dispersing agent Substances 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 19
- 125000005842 heteroatom Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000986 disperse dye Substances 0.000 claims description 8
- 239000003504 photosensitizing agent Substances 0.000 claims description 8
- 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 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- DKTOWFDVEJQWPF-UHFFFAOYSA-N 1-ethylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC DKTOWFDVEJQWPF-UHFFFAOYSA-N 0.000 claims description 4
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- IXLDIJPRDDUUKL-UHFFFAOYSA-N (dimethylamino)methyl benzoate Chemical compound CN(C)COC(=O)C1=CC=CC=C1 IXLDIJPRDDUUKL-UHFFFAOYSA-N 0.000 claims description 3
- SUDVPELGFZKOMD-UHFFFAOYSA-N 1,2-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C(C)C)C(C(C)C)=CC=C3SC2=C1 SUDVPELGFZKOMD-UHFFFAOYSA-N 0.000 claims description 3
- UYEDESPZQLZMCL-UHFFFAOYSA-N 1,2-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3SC2=C1 UYEDESPZQLZMCL-UHFFFAOYSA-N 0.000 claims description 3
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 claims description 3
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- QZKVUSSYPPWURQ-UHFFFAOYSA-N 1-methylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C QZKVUSSYPPWURQ-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 3
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 3
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 3
- LFBSRCAWTCWNBA-UHFFFAOYSA-N 2-butoxyethyl 4-(methylamino)benzoate Chemical compound C(CCC)OCCOC(C1=CC=C(C=C1)NC)=O LFBSRCAWTCWNBA-UHFFFAOYSA-N 0.000 claims description 3
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 claims description 3
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- ARXVXVOLXMVYIT-UHFFFAOYSA-N 3-methylbutyl 2-(dimethylamino)benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1N(C)C ARXVXVOLXMVYIT-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 3
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000003086 colorant Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 description 46
- 239000000976 ink Substances 0.000 description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229940096522 trimethylolpropane triacrylate Drugs 0.000 description 6
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 4
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 4
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000006146 oximation reaction Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 2
- NFKAWBGFIMBUMB-UHFFFAOYSA-N 1-phenylpentan-2-one Chemical compound CCCC(=O)CC1=CC=CC=C1 NFKAWBGFIMBUMB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 description 1
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- OKJAFMLILOEHQK-UHFFFAOYSA-N 1,1,1-tri(prop-2-enoyloxy)propan-2-yl prop-2-enoate Chemical compound C(C=C)(=O)OC(C(C)OC(C=C)=O)(OC(C=C)=O)OC(C=C)=O OKJAFMLILOEHQK-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- IHJUECRFYCQBMW-UHFFFAOYSA-N 2,5-dimethylhex-3-yne-2,5-diol Chemical compound CC(C)(O)C#CC(C)(C)O IHJUECRFYCQBMW-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical group CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- ZMTHSBHENMSOSL-UHFFFAOYSA-N 3-methylpent-1-yn-3-ol Chemical compound CC(C#C)(CC)O.CC(C#C)(CC)O ZMTHSBHENMSOSL-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- FWTBRYBHCBCJEQ-UHFFFAOYSA-N 4-[(4-phenyldiazenylnaphthalen-1-yl)diazenyl]phenol Chemical compound C1=CC(O)=CC=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 FWTBRYBHCBCJEQ-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 108091005944 Cerulean Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- VAYOSLLFUXYJDT-RDTXWAMCSA-N Lysergic acid diethylamide Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000999 acridine dye Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000008425 anthrones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 150000005125 dioxazines Chemical class 0.000 description 1
- 230000008034 disappearance Effects 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
- OXEQDLQXHZRTAP-UHFFFAOYSA-N ethyl carbamate;prop-2-enenitrile Chemical compound C=CC#N.CCOC(N)=O OXEQDLQXHZRTAP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical class C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 150000002832 nitroso derivatives Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical class C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- QIQITDHWZYEEPA-UHFFFAOYSA-N thiophene-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=CS1 QIQITDHWZYEEPA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 150000003732 xanthenes Chemical class 0.000 description 1
Classifications
-
- 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
- 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
본 발명은 옥심 화합물을 포함하는 광중합 개시제 및 광경화형 잉크 조성물에 관한 것으로, 더욱 상세하게는, 감도가 우수하며, 적은 양으로도 색상 구현이 가능한 옥심 화합물을 포함하는 광중합 개시제 및 광경화형 잉크 조성물에 관한 것이다.The present invention relates to a photopolymerization initiator and a photocurable ink composition comprising an oxime compound, and more particularly, to a photopolymerization initiator and a photocurable ink composition comprising an oxime compound having excellent sensitivity and color realization in a small amount. It is about.
디지털 잉크젯 기술은 현대 산업에서 편리함과 경제성의 이유로 상업용 및 산업용으로 그 용도를 확장해 왔다. 디지털 잉크젯 잉크는 적용되는 솔벤트의 종류에 따라 수성잉크, 용제잉크, 유성잉크로 구분되며, 그 중에서 용제잉크는 광고 배너등에 널리 사용되고 있다. 그러나 용제잉크의 경우 휘발성이 강한 유기용제를 사용하여, 작업자의 안전 및 건강상의 문제를 야기할 수 있는 문제점이 있다. 이에 유기용제를 친환경 유기용제로 대체하여 사용하고 있으나, 여전히 강한 유기용제의 냄새로 인해 작업환경에 문제를 일으키고 있다. 상술한 바와 같은 문제점을 해결하고자 최근에는 광경화형 UV 잉크가 개발 및 판매되고 있으며, 작업자들에게 직접적으로 UV 영역의 빛이 노출되는 문제점을 개선하고자 가시광영역의 광원, 즉 385nm 혹은 395nm를 사용하는 친환경 LED lamp를 적용하였다.Digital inkjet technology has been used in the modern industry for commercial and industrial reasons due to its convenience and economy. Digital inkjet inks are classified into water-based ink, solvent ink, and oil-based ink according to the type of solvent to be applied. Among them, solvent ink is widely used in advertising banners and the like. However, in the case of solvent ink, there is a problem that may cause safety and health problems for workers by using an organic solvent having high volatility. Accordingly, the organic solvent is used as an eco-friendly organic solvent, but it still causes problems in the working environment due to the strong smell of the organic solvent. In order to solve the above-described problems, photo-curable UV inks are recently developed and sold, and eco-friendly light sources in the visible region, that is, 385 nm or 395 nm, are used to improve the problem of light exposure in the UV region directly to workers. LED lamp was applied.
이러한 LED-UV 광경화형 잉크 조성물은 385nm 또는 395nm의 영역에서 광경화가 이루어져 하는데, 기존의 광개시제의 385nm영역 이상에서는 흡수가 낮아 새로운 분야의 개시제가 요구되고 있다. 385~395nm 영역에서 개시하는 효율이 떨어지는 경우 경화속도가 매우 느려져 품질 또는 생산 효율에 악영향을 미칠 수 있다. 이에 고감도 개시제인 옥심에스테르를 적용하여 개선하려는 연구가 진행되고 있으며, 이러한 기술의 일 예가 비특허문헌 1과 특허문헌 1 내지 특허문헌 4에 개시되어 있다. The LED-UV photocurable ink composition is photocured in the region of 385nm or 395nm, and the absorption is low in the 385nm region or more of the existing photoinitiator, and a new field initiator is required. If the starting efficiency in the 385 to 395nm region is low, the curing rate may be very slow, which may adversely affect quality or production efficiency. To this end, research is underway to improve by applying an oxime ester, which is a high-sensitivity initiator, and an example of such a technique is disclosed in Non-Patent Documents 1 and 4 and 4.
비특허문헌 1과 특허문헌 1 내지 특허문헌 4는 모두 옥심에스테르를 포함하는 광경화 조성물을 개시하고 있다.Non-patent document 1 and patent document 1 to patent document 4 all disclose the photocurable composition containing an oxime ester.
그러나, 상술한 바와 같은 특허문헌들은 광경화 조성물의 개시제로 옥심에스테르를 사용하여 감도는 우수하나, 실제 표현하고자 하는 색상 구현이 어려우며, 가격이 고가라서 상업적인 디지털 잉크젯 기술에 적용하기에는 적합하지 않은 문제점이 있다.However, the patent documents as described above are excellent in sensitivity using an oxime ester as an initiator of the photocurable composition, but it is difficult to implement a color to express in reality, and the price is high, so there is a problem that it is not suitable for application in a commercial digital inkjet technology. have.
따라서, 이러한 문제점을 근본적으로 해결할 수 있는 광중합 개시제 및 이를 포함하는 광경화형 잉크 조성물에 대한 요구가 높은 실정이다.Therefore, there is a high demand for a photopolymerization initiator that can fundamentally solve these problems and a photocurable ink composition comprising the same.
본 발명은 옥심 화합물을 포함하는 광중합 개시제 및 광경화형 잉크 조성물을 제공하며, 광중합 개시제로 옥심 화합물을 포함함으로써 높은 감도를 가지면서도 색감이 우수한 광경화형 잉크 조성물을 제공하는 것이다. The present invention provides a photopolymerization initiator and a photocurable ink composition comprising an oxime compound, and provides a photocurable ink composition having high sensitivity and excellent color feeling by including an oxime compound as a photopolymerization initiator.
본 발명의 목적은 이상에서 언급한 목적으로 제한되지 않는다. 본 발명의 목적은 이하의 설명으로 보다 분명해질 것이며, 특허청구범위에 기재된 수단 및 그 조합으로 실현될 것이다.The object of the present invention is not limited to the object mentioned above. The object of the present invention will become more apparent from the following description, and will be realized by means described in the claims and combinations thereof.
본 발명의 일 실시예에 따른 광중합 개시제는 하기 화학식 1로 표시되는 옥심 화합물을 포함한다.Photopolymerization initiator according to an embodiment of the present invention includes an oxime compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, R1은 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬 또는 비치환의 C6-C20 알릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬로 이루어진 군으로부터 선택되고, R2 내지 R6는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C6-C20 아릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬, 할로겐, CN, NO2, NR7R8, SR9, COOR10, COR11, SO2R12으로 이루어진 군으로부터 선택되고, 여기서, 헤테로 원자는 N, O 및 S로 이루어진 군으로부터 선택되며, R7 내지 R12는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄 또는 측쇄 알킬, 및 치환 또는 비치환의 C6-C20 아릴로 이루어진 군으로부터 선택된다.In Formula 1, R 1 is substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl or unsubstituted C 6 -C 20 allyl, Selected from the group consisting of substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, R 2 to R 6 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight, branched or cyclic alkenyl, substituted Or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, halogen, CN, NO 2 , NR 7 R 8 , SR 9 , COOR 10 , COR 11 , SO 2 R 12 is selected from the group consisting of, wherein the hetero atom is selected from the group consisting of N, O and S, and R 7 to R 12 are each independently hydrogen , Substituted or unsubstituted C 1 -C 20 straight or branched chain alkyl, and substituted or unsubstituted C 6 -C 20 aryl.
본 발명의 다른 실시예에 따른 광중합 개시제는 하기 화학식 2로 표시되는 옥심 화합물을 포함한다.Photopolymerization initiator according to another embodiment of the present invention includes an oxime compound represented by the formula (2).
[화학식 2][Formula 2]
상기 화학식 2에서, R1은 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬 또는 비치환의 C6-C20 알릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬로 이루어진 군으로부터 선택되고, R2 내지 R6 및 R13 내지 R16는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C6-C20 아릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬, 할로겐, CN, NO2, NR7R8, SR9, COOR10, COR11, SO2R12으로 이루어진 군으로부터 선택되고, 여기서, 헤테로 원자는 N, O 및 S로 이루어진 군으로부터 선택되며, R7 내지 R12는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄 또는 측쇄 알킬, 및 치환 또는 비치환의 C6-C20 아릴로 이루어진 군으로부터 선택되고, R17은 치환 또는 비치환의 C4-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C4-C20 직쇄 또는 측쇄 알콕시알킬기, 및 치환 또는 비치환의 C6-C20 아릴, 및 치환 또는 비치환의 C7-C20 아릴알킬로 이루어진 군으로부터 선택되며, A는 C, N, O, S 원소로 이루어진 군으로부터 선택된다. In Formula 2, R 1 is substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl or unsubstituted C 6 -C 20 allyl, Selected from the group consisting of substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, R 2 to R 6 and R 13 to R 16 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain, side chain Or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, halogen, CN , NO 2 , NR 7 R 8 , SR 9 , COOR 10 , COR 11 , SO 2 R 12 , wherein the hetero atom is selected from the group consisting of N, O and S, R 7 to R 12 are each independently selected from the group consisting of hydrogen, substituted or unsubstituted C 1 -C 20 straight chain or branched alkyl, and substituted or unsubstituted C 6 -C 20 aryl, and R 17 is substituted or unsubstituted C 4 -C 20 straight chain, branched or cyclic alkyl, substituted or unsubstituted C 4 -C 20 straight chain or branched alkoxyalkyl group, and It is selected from the group consisting of substituted or unsubstituted C 6 -C 20 aryl, and substituted or unsubstituted C 7 -C 20 arylalkyl, and A is selected from the group consisting of C, N, O, and S elements.
이때, 상기 옥심 화합물은At this time, the oxime compound is
본 발명의 또 다른 실시예에 따른 광경화형 잉크 조성물은 화학식 1 또는 화학식 2로 표시되는 광중합 개시제를 포함한다.The photocurable ink composition according to another embodiment of the present invention includes a photopolymerization initiator represented by Formula 1 or Formula 2.
이때, 상기 조성물은 광중합 개시제 1~20중량%, 에틸렌계 불포화 결합을 가지는 화합물 40~90중량%, 에틸렌 불포화 결합을 다관능으로 가지는 화합물 5~30중량%, 분산액 5~15중량% 및 분산제, 광증감제 및 이들의 조합으로부터 선택되는 첨가제 0.01~5중량%를 포함할 수 있다.At this time, the composition is 1 to 20% by weight of a photopolymerization initiator, 40 to 90% by weight of a compound having an ethylenically unsaturated bond, 5 to 30% by weight of a compound having a polyfunctional ethylenically unsaturated bond, 5 to 15% by weight of a dispersion, and a dispersant, It may contain 0.01 to 5% by weight of additives selected from photosensitizers and combinations thereof.
그리고, 상기 광중합 개시제는 벤질, 벤조인에테르, 벤조인 부틸에테르, 벤조인프로필에테르, 벤조페논, 3'-디메틸-4-메톡시벤조페논, 벤조일벤조산, 벤조일벤조산의 에스테르화물, 4-벤조일-4'-메틸디페닐설파이드, 벤질 디메틸케탈, 2-부톡시에틸-4-메틸아미노벤조에이트, 클로로티옥산톤, 메틸티옥산톤, 에틸티옥산톤, 이소프로필티옥산톤, 디메틸티옥산톤, 디에틸티옥산톤, 디이소프로필티옥산톤, 디메틸아미노메틸벤조에이트, 디메틸아미노벤조산 이소아밀에스테르, 1- (4-도데실페닐)-2-하이드록시-2-메틸프로판-1-온, 1-하이드록시사이클로헥실페닐 케톤, 2-하이드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 메틸벤조일포름에이트, 2-메틸-1- (4-메틸티오페닐) -2-모폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄-1-온, 2.2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비스이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라-(4-메톡시페닐)비스이미다졸, 디페닐(2,4,6-(트리메틸벤조일))포스핀 옥사이드, 페닐비스(2,4,6-트리메틸벤조일)포스핀 옥사이드 및 이들의 조합으로부터 선택되는 1종을 더 포함할 수 있다.And, the photopolymerization initiator is benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3'-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, esterification of benzoylbenzoic acid, 4-benzoyl- 4'-methyldiphenylsulfide, benzyl dimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methyl thioxanthone, ethyl thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone , Diethyl thioxanthone, diisopropyl thioxanthone, dimethylaminomethylbenzoate, dimethylaminobenzoic acid isoamyl ester, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1- On, methylbenzoylformate, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-Butan-1-one, 2.2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetra-(4-methoxyphenyl)bisimidazole, diphenyl(2,4,6-(trimethylbenzoyl))phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl ) Phosphine oxide and a combination thereof.
그리고, 상기 에틸렌계 불포화 결합을 가지는 화합물은 아크릴산, 메타아크릴산, 아크릴산 에스테르, 메타크릴산 에스테르, 스틸렌, 아크릴로니트릴 및 이들의 조합으로부터 선택되는 1종일 수 있다.In addition, the compound having an ethylenically unsaturated bond may be one selected from acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, acrylonitrile, and combinations thereof.
또한, 상기 에틸렌 불포화 결합을 다관능으로 가지는 화합물은 디펜타에리스리톨 아크릴레이트, 글리세롤 트리아크릴레이트, 펜타에리스리톨 트리테트라아크릴레이트, 트리메틸롤프로판에톡시 트리아크릴레이트, 트리메틸롤프로판 트리아크릴레이트, 디트리메틸롤프로판 테트라아크릴레이트 및 이들의 조합으로부터 선택되는 1종일 수 있다.In addition, the compound having a polyfunctional ethylenically unsaturated bond is dipentaerythritol acrylate, glycerol triacrylate, pentaerythritol tritetraacrylate, trimethylolpropaneethoxy triacrylate, trimethylolpropane triacrylate, ditrimethylol And propane tetraacrylate and combinations thereof.
여기서, 상기 분산액은 용제 70~90중량%, 분산염료 1~20중량% 및 분산제 1~10중량%를 포함할 수 있다.Here, the dispersion may include 70 to 90% by weight of the solvent, 1 to 20% by weight of the disperse dye, and 1 to 10% by weight of the dispersant.
이때, 상기 분산제는 음이온성 계면활성제, 비이온성 계면활성제, 양쪽성 계면활성제, 고분자계 분산제 및 이들의 조합으로부터 선택되는 1종일 수 있다.In this case, the dispersant may be one selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, polymer-based dispersants, and combinations thereof.
본 발명에 따른 광경화형 잉크 조성물은 옥심 화합물을 포함하는 광중화 개시제를 포함함으로써 다른 조성물에 비하여 감도가 우수하며, LED UV lamp의 조건 하에서 적은 양으로도 색상 구현이 가능할 뿐 아니라 디지털 프린팅 외에 디스플레이 산업 등 다양하게 적용 가능한 이점이 있다.The photo-curable ink composition according to the present invention has a superior sensitivity compared to other compositions by including a photo-neutralization initiator containing an oxime compound, and it is possible to implement a color in a small amount under the conditions of an LED UV lamp as well as display industry besides digital printing. There are various applicable advantages.
또한, 본 발명에 따른 광경화 잉크 조성물은 보존 안정성이 우수하므로 보존 상태에서 중합이 발생되지 않고, 친환경 LED UV lamp에서 단시간에 효율적으로 중합이 가능한 이점이 있다.In addition, since the photocurable ink composition according to the present invention has excellent storage stability, polymerization does not occur in a storage state, and there is an advantage in that polymerization can be efficiently performed in a short time in an eco-friendly LED UV lamp.
이상의 본 발명의 목적들, 다른 목적들, 특징들 및 이점들은 첨부된 도면과 관련된 이하의 바람직한 실시예들을 통해서 쉽게 이해될 것이다. 그러나 본 발명은 여기서 설명되는 실시예들에 한정되지 않고 다른 형태로 구체화될 수도 있다. 오히려, 여기서 소개되는 실시예들은 개시된 내용이 철저하고 완전해질 수 있도록 그리고 통상의 기술자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 제공되는 것이다.The above objects, other objects, features and advantages of the present invention will be readily understood through the following preferred embodiments associated with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete and that the spirit of the present invention is sufficiently conveyed to those skilled in the art.
본 발명의 광중합 개시제는 화학식 1 또는 화학식 2로 표시되는 옥심 화합물을 포함한다.The photopolymerization initiator of the present invention includes an oxime compound represented by Formula 1 or Formula 2.
화학식 1은 하기와 같은 구조를 가진다.Formula 1 has the following structure.
상기 화학식 1에서,In Chemical Formula 1,
R1은 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬 또는 비치환의 C6-C20 알릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬로 이루어진 군으로부터 선택되고,R 1 is substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl or unsubstituted C 6 -C 20 allyl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl,
R2 내지 R6는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C6-C20 아릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬, 할로겐, CN, NO2, NR7R8, SR9, COOR10, COR11, SO2R12으로 이루어진 군으로부터 선택되고, 여기서, 헤테로 원자는 N, O 및 S로 이루어진 군으로부터 선택되며, R7 내지 R12는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄 또는 측쇄 알킬, 및 치환 또는 비치환의 C6-C20 아릴로 이루어진 군으로부터 선택된다.R 2 to R 6 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, halogen, CN, NO 2 , NR 7 R 8 , SR 9 , COOR 10 , COR 11 , SO 2 R 12 Wherein, the hetero atom is selected from the group consisting of N, O and S, R 7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain or branched alkyl, and substituted or unsubstituted C 6 -C 20 aryl.
또한 R3, R4는 아래 구조와 같이 이웃한 아릴과 브릿지를 통한 연결이 될 수 있다. In addition, R 3 and R 4 may be connected through a bridge with neighboring aryl as shown below.
화학식 2는 하기와 같은 구조를 가진다.Formula 2 has the following structure.
화학식 2에서,In Formula 2,
R1은 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬 또는 비치환의 C6-C20 알릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬로 이루어진 군으로부터 선택되고,R 1 is substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl or unsubstituted C 6 -C 20 allyl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl,
R2 내지 R6 및 R13 내지 R16는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C6-C20 아릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬, 할로겐, CN, NO2, NR7R8, SR9, COOR10, COR11, SO2R12으로 이루어진 군으로부터 선택되고, 여기서, 헤테로 원자는 N, O 및 S로 이루어진 군으로부터 선택되며, R7 내지 R12는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄 또는 측쇄 알킬, 및 치환 또는 비치환의 C6-C20 아릴로 이루어진 군으로부터 선택되고,R 2 to R 6 and R 13 to R 16 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl, Substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, halogen, CN, NO 2 , NR 7 R 8 , SR 9 , COOR 10 , COR 11 , SO 2 R 12 , wherein the hetero atom is selected from the group consisting of N, O and S, and R 7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain or branched alkyl, And substituted or unsubstituted C 6 -C 20 aryl,
R17은 치환 또는 비치환의 C4-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C4-C20 직쇄 또는 측쇄 알콕시알킬기, 및 치환 또는 비치환의 C6-C20 아릴, 및 치환 또는 비치환의 C7-C20 아릴알킬로 이루어진 군으로부터 선택되며,R 17 is a substituted or unsubstituted C 4 -C 20 straight chain, branched or cyclic alkyl, substituted or unsubstituted C 4 -C 20 straight chain or branched alkoxyalkyl group, and Selected from the group consisting of substituted or unsubstituted C 6 -C 20 aryl, and substituted or unsubstituted C 7 -C 20 arylalkyl,
A는 C, N, O, S 원소로 이루어진 군으로부터 선택된다.A is selected from the group consisting of C, N, O, and S elements.
구체적으로, 본 발명에 따른 화학식 1 또는 화학식 2로 표시되는 옥심 화합물은 표 1의 화학식 1-1 내지 화학식 1-21로부터 선택될 수 있으나, 이들로 한정되는 것은 아니다.Specifically, the oxime compound represented by Chemical Formula 1 or Chemical Formula 2 according to the present invention may be selected from Chemical Formulas 1-1 to 1-21 in Table 1, but is not limited thereto.
본 발명에 따른 화학식 1의 화합물은 표준 화학 교과서(예를들면, J.March, Advanced Or ganic chemistry, 4th Edition, Wiley Interscience, 1992) 또는 전문적인 모노그래프(예를 들면, S.R. Sandler & W. Karo. Or ganic functional group preparations, Vol. 3. Academic Press)에 기재된 여러가지 방법에 얻을 수 있다.Compounds of formula 1 according to the present invention can be prepared by standard chemistry textbooks (eg, J.March, Advanced Or ganic chemistry, 4 th Edition, Wiley Interscience, 1992) or professional monographs (eg, SR Sandler & W. Karo. Or ganic functional group preparations, Vol. 3. Academic Press).
하기 반응식 1과 같이 아질산 알칸과 염산을 이용하여 쉽게 제조할 수 있으나, 이에 한정되는 것은 아니다.As shown in Reaction Scheme 1 below, it can be easily prepared by using nitrite alkanes and hydrochloric acid, but is not limited thereto.
[반응식 1][Scheme 1]
상기 반응은 용매로 THF, 아세톤, MC(methylene chlororide), DMF, 에틸 아세테이트(ethyl acetate) 및 이들의 조합으로 이루어진 군에서 선택되는 적어도 1종을 사용할 수 있으며, 0~50℃, 바람직하게는 0~20℃의 온도 조건 하에서 실시될 수 있다. 여기서 알칸은 부탄 혹은 펜탄, 헥산일 수 있으나, 이에 한정되는 것은 아니다.As the solvent, at least one selected from the group consisting of THF, acetone, methylene chlororide (MC), DMF, ethyl acetate, and combinations thereof may be used as a solvent, and 0 to 50°C, preferably 0 It can be carried out under a temperature condition of ~20 ℃. Here, the alkane may be butane, pentane, or hexane, but is not limited thereto.
이하에서는, 본 발명의 광경화형 잉크 조성성분을 설명한다.Hereinafter, the photocurable ink composition component of the present invention will be described.
본 발명의 광경화형 잉크 조성물은 에틸렌계 불포화 결합을 가지는 화합물, 우렌탄계 소중합체, 광중합 개시제, 에틸렌계 불포화결합을 다관능으로 가지는 화합물, 분산액 및 첨가제를 포함한다.The photocurable ink composition of the present invention includes a compound having an ethylenically unsaturated bond, a urethane-based oligomer, a photopolymerization initiator, a compound having an ethylenically unsaturated bond multifunctionally, a dispersion, and an additive.
(1) 에틸렌계 불포화결합을 가지는 화합물(1) Compounds having an ethylenically unsaturated bond
에틸렌계 불포화결합을 가지는 화합물은 종래 광경화형 조성물에 이용되는 화합물로서, 바람직하게는 2-히드록시 에틸(메타)아크릴레이트, 2-히드록시 프로필(메타)아크릴레이트, 시클로 헥실(메타)아크릴레이트, 테트라하이드로퍼퓨릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 폴리에틸렌 글리콜딘(메타)아크릴레이트, 펜타 에리스리톨테트라(메타)아크릴레이트, 펜타에리스톨트리(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리에틸렌글리콜(메타)아크릴레이트, 디펜타에리스리톨아크릴레이트, 글리세롤(메타)아크릴레이트, 멜라민(메타)아크릴레이트, 에폭시(메타)아크릴레이트 등의 각종 아크릴산 에스테르, 메타크릴산 에스테르, (메타)아크릴산, 스틸렌, 아크릴로니트릴 에틸렌계 불포화결합을 가지는 우레탄계 소중합체 및 이들의 조합으로부터 선택되는 적어도 1종, 바람직하게는 비스페놀-A형 에폭시디(메타)아크릴레이트, 비스페놀-플루오렌형 에폭시디(메타)아크릴레이트 및 이들의 조합으로부터 선택되는 적어도 1종 일 수 있다. 우레탄계 소중합체는 직쇄 혹은 환상 지방족 또는 방향족으로 구성되어 있고, 상업적으로 제조되어 판매되고 있는 제품을 사용할 수 있으며, 일예로 NeoRad series, Agi-syn series(이상 AGI사), BR series, BRT series (이상 Dymax사), EBECRYL series(이상Cytec 사) 및 이들의 조합으로부터 선택되는 적어도 1종을 사용할 수 있다. 이러한 에틸렌계 불포화결합을 가지는 화합물은 전체 중량%에 대하여, 40~90중량%, 바람직하게는 50~80중량%포함될 수 있다.The compound having an ethylenically unsaturated bond is a compound used in a conventional photocurable composition, preferably 2-hydroxy ethyl (meth)acrylate, 2-hydroxy propyl (meth)acrylate, cyclohexyl (meth)acrylate , Tetrahydroperfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethylene glycoldine (meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylol Various acrylic acid esters such as propane tri(meth)acrylate, triethylene glycol (meth)acrylate, dipentaerythritol acrylate, glycerol (meth)acrylate, melamine (meth)acrylate, epoxy (meth)acrylate, meta At least one selected from a acrylate ester, (meth)acrylic acid, styrene, an acrylonitrile urethane-based oligomer having an ethylenically unsaturated bond, and combinations thereof, preferably bisphenol-A type epoxydi(meth)acrylate, bisphenol -Fluorene-type epoxy di (meth) acrylate and may be at least one selected from combinations thereof. The urethane-based oligomer is composed of straight chain or cyclic aliphatic or aromatic, and commercially manufactured and sold products can be used.For example, NeoRad series, Agi-syn series (above AGI), BR series, BRT series (above) Dymax), EBECRYL series (above Cytec), and combinations thereof, can be used. The compound having an ethylenically unsaturated bond may be included in an amount of 40 to 90% by weight, preferably 50 to 80% by weight, based on the total weight%.
(2) 에틸렌계 불포화결합을 다관능으로 가지는 화합물(2) Compounds having polyfunctional ethylenically unsaturated bonds
에틸렌계 불포화결합을 다관능으로 가지는 화합물은 경도 상승을 위하여 첨가하는 물질로, 에틸렌계 불포화결합의 갯수가 3개 내지 6개일 수 있다. 구체적으로, 디펜타에리스리톨 아크릴레이트, 글리세롤 트리아크릴레이트, 펜타에리스리톨 트리테트라아크릴레이트, 트리메틸롤프로판에톡시 트리아크릴레이트, 트리메틸롤프로판 트리아크릴레이트, 디트리메틸롤프로판 테트라아크릴레이트 및 이들의 조합으로부터 선택되는 적어도 1종일 수 있다. 이러한 에틸렌계 불포화결합을 다관능으로 가지는 화합물은 전체 중량%에 대하여, 5~30중량%, 바람직하게는 10~25중량% 포함될 수 있다.A compound having an ethylenically unsaturated bond as a polyfunctional compound is a material added to increase hardness, and the number of ethylenically unsaturated bonds may be 3 to 6. Specifically, selected from dipentaerythritol acrylate, glycerol triacrylate, pentaerythritol tritetraacrylate, trimethylolpropaneethoxy triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate and combinations thereof Can be at least one. The compound having the ethylenically unsaturated bond as a polyfunctional compound may be included in an amount of 5 to 30% by weight, preferably 10 to 25% by weight, based on the total weight%.
(3) 광중합 개시제(3) Photopolymerization initiator
광중합 개시제는 본 발명의 옥심 화합물과 그 외에, 필요에 따라서 다른 광중합 개시제를 병용하여 사용가능하며, 이에 현저한 상승효과를 발휘할 수 있다. The photopolymerization initiator can be used in combination with the oxime compound of the present invention and other photopolymerization initiators, if necessary, and can exhibit a remarkable synergistic effect.
본 발명의 옥심 화합물과 함께 사용 가능한 광중합 개시제는 종래 공지의 화합물을 이용하는 것이 가능하며, 바람직한 예로는, 벤질, 벤조인에테르, 벤조인 부틸에테르, 벤조인프로필에테르, 벤조페논, 3'-디메틸-4-메톡시벤조페논, 벤조일벤조산, 벤조일벤조산의 에스테르화물, 4-벤조일-4'-메틸디페닐설파이드, 벤질 디메틸케탈, 2-부톡시에틸-4-메틸아미노벤조에이트, 클로로티옥산톤, 메틸티옥산톤, 에틸티옥산톤, 이소프로필티옥산톤, 디메틸티옥산톤, 디에틸티옥산톤, 디이소프로필티옥산톤, 디메틸아미노메틸벤조에이트, 디메틸아미노벤조산 이소아밀에스테르, 1- (4-도데실페닐)-2-하이드록시-2-메틸프로판-1-온, 1-하이드록시사이클로헥실페닐 케톤, 2-하이드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 메틸벤조일포름에이트, 2-메틸-1- (4-메틸티오페닐) -2-모폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄-1-온, 2.2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비스이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라-(4-메톡시페닐)비스이미다졸, 디페닐(2,4,6-(트리메틸벤조일))포스핀 옥사이드, 페닐비스(2,4,6-트리메틸벤조일)포스핀 옥사이드 및 이들의 조합으로부터 선택되는 적어도 1종일 수 있다. 이러한 광중합 개시제는 전체 중량%에 대하여, 1~20중량%, 바람직하게는 1~15중량% 포함될 수 있다.The photopolymerization initiator usable with the oxime compound of the present invention can use a conventionally known compound, and preferred examples include benzyl, benzoin ether, benzoin butyl ether, benzoinpropyl ether, benzophenone, and 3'-dimethyl-. 4-methoxybenzophenone, benzoylbenzoic acid, esterified products of benzoylbenzoic acid, 4-benzoyl-4'-methyldiphenylsulfide, benzyl dimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, Methyl thioxanthone, ethyl thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, diisopropyl thioxanthone, dimethylaminomethylbenzoate, dimethylaminobenzoic acid isoamyl ester, 1- ( 4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2.2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Phenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra-(4-methoxyphenyl)bisimidazole, diphenyl(2,4,6- (Trimethylbenzoyl))phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and combinations thereof. The photopolymerization initiator may be included in an amount of 1 to 20% by weight, preferably 1 to 15% by weight, based on the total weight%.
(4) 분산액(4) dispersion
분산액은 분산염료, 분산제 및 용제를 포함하며, 전체 중량%에 대하여, 5~15중량%, 바람직하게는 7~13중량% 포함될 수 있다.The dispersion liquid includes a disperse dye, a dispersant, and a solvent, and may be included in an amount of 5 to 15% by weight, preferably 7 to 13% by weight, based on the total weight%.
분산염료는 안료, 염료, 천연 색소 등을 포함할 수 있으며, 이들 분산염료는 단독 또는 2종 이상을 혼합하여 사용할 수 있다.Disperse dyes may include pigments, dyes, and natural pigments, and these disperse dyes may be used alone or in combination of two or more.
안료는 니트로소 화합물; 니트로 화합물; 아조 화합물; 디아조 화합물; 크산텐 화합물; 퀴놀린 화합물; 안트라퀴논 화합물; 쿠마린 화합물; 프탈로시아닌 화합물; 이소인돌리논 화합물; 이소인돌린 화합물; 퀴나크리돈 화합물; 안탄트론 화합물; 페리논 화합물; 페릴렌 화합물; 디케토피롤로피롤 화합물; 티오인디고 화합물; 디옥사진 화합물; 트리페닐메탄 화합물; 퀴노프탈론 화합물; 나프탈렌테트라카르본산; 아조 염료, 시아닌 염료의 금속 착체 화합물; 레이크(lake) 안료; 퍼니스(furnace)법, 채널(channel)법 또는 써멀(thermal)법에 의해 얻어지는 카본블랙, 혹은 아세틸렌블랙, 케첸블랙 또는 램프블랙 등의 카본블랙; 상기 카본블랙을 에폭시 수지로 조정 또는 피복한 것, 상기 카본블랙을 미리 용매 중에서 수지로 분산 처리하여 20~200mg/g의 수지를 흡착시킨 것, 상기 카본블랙을 산성 또는 알칼리성 표면 처리한 것, 평균 입경이 8nm 이상이고 DBP 흡유량(吸油量)이 90ml/100g 이하인 것, 950℃에서의 휘발분 중의 CO 및 CO2에서 산출한 전체 산소량이 카본블랙의 표면적 100㎡당 9mg 이상인 것; 흑연, 흑연화 카본블랙, 활성탄, 탄소섬유, 카본나노튜브, 카본마이크로코일, 카본나노혼, 카본에어로겔, 풀러린(fullerene); 아닐린블랙, 피그먼트 블랙 7, 티탄블랙; 산화크롬 그린, 밀로리 블루, 코발트 그린, 코발트 블루, 망간계, 페로시안화물, 인산염 군청, 감청, 울트라마린, 세룰리안 블루, 피리디안, 에메랄드 그린, 황산납, 황색납, 아연황, 철단(적색 산화철(Ⅲ)), 카드뮴 레드, 합성 철흑, 앰버 등의 유기 또는 무기 안료를 사용할 수 있다. 이들 안료는 단독으로, 또는 2종 이상을 조합하여 사용할 수 있으며, 상술한 안료 종류로 제한되지 않는다. 상업적으로 구입 가능한 안료로는 예를 들면 피그먼트 레드 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; 피그먼트 오렌지 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; 피그먼트 옐로우 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 166, 168, 175, 180, 185; 피그먼트 그린 7, 10, 36; 피그먼트 블루 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; 피그먼트 바이올렛 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 일 수 있다.The pigment is a nitroso compound; Nitro compounds; Azo compounds; Diazo compounds; Xanthene compounds; Quinoline compounds; Anthraquinone compounds; Coumarin compounds; Phthalocyanine compounds; Isoindolinone compound; Isoindoline compounds; Quinacridone compound; Anthrone compounds; Perinone compounds; Perylene compounds; Diketopyrrolopyrrole compound; Thioindigo compounds; Dioxazine compounds; Triphenylmethane compound; Quinophthalone compounds; Naphthalene tetracarboxylic acid; Metal complex compounds of azo dyes and cyanine dyes; Lake pigments; Carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black; The carbon black is adjusted or coated with an epoxy resin, the carbon black is pre-dispersed with a resin in a solvent to adsorb 20 to 200 mg/g of the resin, and the carbon black is treated with an acidic or alkaline surface, on average A particle size of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less, and a total amount of oxygen calculated from CO and CO 2 in volatile matter at 950° C. of 9 mg or more per 100 m 2 of carbon black; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; Aniline black, pigment black 7, titanium black; Chromium Oxide Green, Milori Blue, Cobalt Green, Cobalt Blue, Manganese, Ferrocyanide, Phosphate Ultramarine, Royal Blue, Ultramarine, Cerulean Blue, Pyridian, Emerald Green, Lead Sulfate, Yellow Lead, Zinc Sulfur, Iron ( Organic or inorganic pigments such as red iron oxide (III)), cadmium red, synthetic iron black, and amber can be used. These pigments may be used alone or in combination of two or more, and are not limited to the aforementioned types of pigments. Pigments commercially available include, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119 , 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114 , 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50.
염료는 아조 염료, 안트라퀴논 염료, 인디고이드 염료, 트리아릴메탄 염료, 크산텐 염료, 알리자린 염료, 아크리딘 염료, 스틸벤 염료, 티아졸 염료, 나프톨 염료, 퀴놀린 염료, 니트로 염료, 인다민 염료, 옥사진 염료, 프탈로시아닌 염료, 시아닌 염료 등이 포함될 수 있으며, 분산용액 제조 시 이들을 복수로 혼합하여 사용할 수 있다. The dyes are azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes , Oxazine dye, phthalocyanine dye, cyanine dye, and the like, and may be used by mixing a plurality of them when preparing a dispersion solution.
이러한 분산염료는 분산액 전체중량%에 대하여, 1~20중량%, 바람직하게는 10~20중량% 포함될 수 있다. 상술한 분산염료의 수치한정은 원하는 색을 발현하기 위한 바람직한 범위로 이보다 지나치게 많거나 적은 양이 포함될 경우, 본원발명이 의도하는 적절한 색을 가지는 광경화 잉크 조성물의 구현이 어려울 수 있으므로 바람직하지 못하다.The dispersion dye may be included in an amount of 1 to 20% by weight, preferably 10 to 20% by weight, based on the total weight of the dispersion. The numerical limitation of the above-described disperse dye is not preferable because it may be difficult to implement a photocurable ink composition having an appropriate color intended by the present invention when an excessively large amount or less amount is included in a preferred range for expressing a desired color.
분산제는 유무기 안료 등의 색재를 분산시키기 위해 첨가하는 물질로, 음이온성 계면활성제, 비이온성 계면활성제, 양쪽성 계면활성제, 고분자계 분산제 및 이들의 조합으로부터 선택되는 1종일 수 있으나 색재를 안정화시킬 수 있는 물질이라면 그 사용을 크게 제한하지 않는다. 시판되는 분산제로는 빅케미사 제품인 BYK 시리즈(폴리디메틸실록산(polydimethylsiloxane)) 등을 사용할 수 있고, 고분자계 분산제는 염기성 관능기를 가지는 폴리에스테르(polyester), 폴리에테르(polyether), 폴리우레탄(polyurethane) 및 이들의 조합으로부터 선택되는 1종일 수 있으며, 여기서, 염기성 관능기로 질소원자를 가질 수 있고, 질소원자를 가지는 관능기가 아민, 및/또는 그 4급 염이며, 아민기가 1~100mgKOH/g일 수 있다. 이러한 분산제는 분산액 전체중량%에 대하여, 1~10중량%, 바람직하게는 1~5중량% 포함될 수 있다.Dispersant is a material added to disperse colorants such as organic and inorganic pigments, and may be one selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, polymer-based dispersants, and combinations thereof, but may stabilize colorants If possible, its use is not greatly limited. As a commercially available dispersant, a BYK series (polydimethylsiloxane) manufactured by BIC Chemie may be used, and a polymer-based dispersant may include polyester, polyether, polyurethane and polyurethane having basic functional groups. It may be one selected from a combination of these, where a basic functional group may have a nitrogen atom, a functional group having a nitrogen atom is an amine, and/or a quaternary salt thereof, and the amine group may be 1 to 100 mgKOH/g. . The dispersant may be included in an amount of 1 to 10% by weight, preferably 1 to 5% by weight, based on the total weight of the dispersion.
용제로는 에틸렌계 불포화결합을 가지는 화합물을 사용할 수 있으며, 상기에서 상세하게 설명하였으므로 생략하기로 한다. 용제는 분산액 전체중량%에 대하여, 70~90중량%, 바람직하게는 75~85중량% 포함될 수 있다.As the solvent, a compound having an ethylenically unsaturated bond may be used, and since it has been described in detail above, it will be omitted. The solvent may be included in an amount of 70 to 90% by weight, preferably 75 to 85% by weight, based on the total weight of the dispersion.
(5) 첨가제(5) Additive
첨가제는 분산제, 연쇄 이동제, 증감제, 산화방지제, 안정제, 광증감제를 포함하며, 첨가제는 광경화형 잉크 조성물에서 수지 조성물의 물성을 저해하지 않는 범위 내에서 일정량 첨가될 수 있으며, 전체 중량%에 대하여, 0.001~5중량% 포함될 수 있다.Additives include dispersants, chain transfer agents, sensitizers, antioxidants, stabilizers, photosensitizers, additives can be added in a certain amount within a range that does not impair the physical properties of the resin composition in the photocurable ink composition, the total weight% With respect to, it may be included 0.001 to 5% by weight.
분산제는 유무기 안료 등의 색재를 분산시키기 위해 첨가하는 물질로, 음이온성 계면활성제, 비이온성 계면활성제, 양쪽성 계면활성제, 고분자계 분사제 및 이들의 조합으로부터 선택되는 1종일 수 있으나 색재를 안정화시킬 수 있는 물질이라면 그 사용을 크게 제한하지 않는다. 계면활성제로는 폴리옥시에틸렌에테르과 같은 비이온 계면활성제를 주로 사용하고, 아세틸렌글리콜계, 불소계, 실리콘계 계면활성제 및 비실리콘계 계면활성제로 이루어진 군으로부터 선택되는 1종, 구체적으로는 2,4,7,9-테트라메틸-5-데신-4,7-디올(2,4,7,9-Tetramethyl-5-decyne-4,7-diol)계열 계면활성제, 1-하이드록시-1-메틸에틸 아세틸린(1-Hydroxy-1-methylethyl acetylene), 2,5-디메틸-3-헥신-2,5-디올(2,5-Dimethyl-3-hexyne-2,5-diol), 3-메틸-1-펜틴-3-올(3-Methyl-1-pentyn-3-ol), 아세틸렌 글리콜 유도체(acetylene glycol derivative), 폴리에틸렌글리콜 아세틸렌 글리콜 에테르(Polyethylene glycol acetylene glycol ether), 2,4,7,9-테트라메틸-5-데신-4,7-디올-비스폴리옥시에틸렌 에테르(2,4,7,9-Tetramethyl-5-decyne-4,7-dilo-bispolyoxyethylene ether), 아세틸렌 글리콜형 계면활성제(acetylene glycol-type surfactant) 및 이들의 조합으로부터 선택되는 1종일 수 있으며, 상업적으로 구입이 가능한 계면활성제로는 BYK306, 307, 333, 341, 345, 346, 348(BYK Co., Ltd) 등이 있다. 고분자계 분산제는 염기성 관능기를 가지는 폴리에스테르, 폴리에테르, 또는 폴리우레탄으로 이루어지는 고분자 분산제, 염기성 관능기로서 질소원자를 가지며, 질소원자를 가지는 관능기가 아민, 및/또는 그 4급 염이며, 아민기가 1~100mgKOH/g인 것이 바람직하다. 이러한 분산제는 전체중량%에 대하여, 0.001~2중량% 포함될 수 있다.Dispersant is a material added to disperse colorants such as organic and inorganic pigments, and may be one selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, polymer propellants, and combinations thereof, but stabilizes colorants If the substance can be made, its use is not greatly limited. As the surfactant, a nonionic surfactant such as polyoxyethylene ether is mainly used, and one type selected from the group consisting of acetylene glycol-based, fluorine-based, silicone-based surfactants, and non-silicone-based surfactants, specifically 2,4,7, 9-tetramethyl-5-decine-4,7-diol (2,4,7,9-Tetramethyl-5-decyne-4,7-diol)-based surfactant, 1-hydroxy-1-methylethyl acetyline (1-Hydroxy-1-methylethyl acetylene), 2,5-dimethyl-3-hexine-2,5-diol (2,5-Dimethyl-3-hexyne-2,5-diol), 3-methyl-1- Pentyn-3-ol (3-Methyl-1-pentyn-3-ol), acetylene glycol derivative, polyethylene glycol acetylene glycol ether, 2,4,7,9-tetra Methyl-5-decine-4,7-diol-bispolyoxyethylene ether (2,4,7,9-Tetramethyl-5-decyne-4,7-dilo-bispolyoxyethylene ether), acetylene glycol surfactant -type surfactant) and combinations thereof, and commercially available surfactants include BYK306, 307, 333, 341, 345, 346, 348 (BYK Co., Ltd). The polymer-based dispersant is a polymer dispersant composed of a polyester, polyether, or polyurethane having a basic functional group, a nitrogen atom as a basic functional group, a functional group having a nitrogen atom is an amine, and/or a quaternary salt thereof, and an amine group 1 It is preferably ~100 mgKOH/g. The dispersant may be included in an amount of 0.001 to 2% by weight based on the total weight%.
광증감제는 반응속도를 증가 또는 감소시켜 반응전후에서 같은 상태에 있는 물질로, 균일 촉매 또는 불균일 촉매일 수 있으며, 바람직하게는 2,4-디에틸티오크산톤일 수 있다. 이러한 광증감제는 전체중량%에 대하여, 0.1~3중량% 포함될 수 있다.The photosensitizer is a material in the same state before and after the reaction by increasing or decreasing the reaction rate, and may be a homogeneous catalyst or a heterogeneous catalyst, and preferably 2,4-diethylthioxanthone. The photosensitizer may be included in an amount of 0.1 to 3% by weight based on the total weight%.
상술한 바와 같은 광중합 개시제를 포함하는 광경화 잉크 조성물은 다른 조성물에 비하여 감도가 우수하여 LED-UV lamp의 조건하에서 상대적으로 적은 양으로도 우수한 경화성을 얻을 수 있다. 또한, 색상이 구현되는 UV 잉크에서 적은 양을 사용함으로써 색순도가 다른 광중합 개시제에 비하여 월등히 우수하며, 디지털 프린팅 응용 외에도 디스플레이 산업등의 다양한 산업전반에 적용 가능하다.The photocurable ink composition comprising the photopolymerization initiator as described above has excellent sensitivity compared to other compositions, and thus can obtain excellent curability even in a relatively small amount under the conditions of the LED-UV lamp. In addition, by using a small amount of UV ink in which color is realized, color purity is superior to that of other photopolymerization initiators, and it can be applied to various industries such as display industry as well as digital printing applications.
이러한 광경화형 잉크 조성물은 디지털 잉크젯 프린터를 이용하여 다양한 매체 기판상에 분사되며, 매체 기판은 매끄럽거나 거친 평면, 또는 채용되는 특정 목적에 적합한 특정의 다른 형상을 가질 수 있다. 매체 기판은 약 0.1mm 내지 약 10mm의 범위, 또는 약 1mm내지 약 5mm의 범위의 두께를 가질 수 있고, 매체기판은 필름, 플레이트, 보드, 또는 시트의 형태일 수 있으나, 이것으로 한정하는 것은 아니다. 이러한 매체 기판은 플라스틱 기판, 예를 들면 폴리에틸렌 테레프탈레이트, 폴리에틸렌, 폴리스티렌, 폴리카보이네이트, 아크릴릭, PVC, 종이로 구성될 수 있을 뿐만 아니라 유리도 가능하다.These photocurable ink compositions are sprayed onto various media substrates using a digital inkjet printer, and the media substrates can have a smooth or rough plane, or any other shape suitable for the particular purpose employed. The media substrate may have a thickness ranging from about 0.1 mm to about 10 mm, or from about 1 mm to about 5 mm, and the media substrate may be in the form of a film, plate, board, or sheet, but is not limited thereto. . These media substrates can be composed of plastic substrates, for example polyethylene terephthalate, polyethylene, polystyrene, polycarbonate, acrylic, PVC, paper, as well as glass.
제조예 1: 옥심 화합물 합성Preparation Example 1: Synthesis of oxime compounds
옥심 화합물의 합성공정은 HNO3를 이용한 Nitration, Friedel Craft 반응을 이용한 Acylation, a-keto oxime을 제조하기 위한 Isoamyl nitrite를 이용한 Oximation 공정으로 실시하였다.The synthesis process of the oxime compound was carried out by Nitration using HNO 3 , Acylation using the Friedel Craft reaction, and Oximation using Isoamyl nitrite to prepare a-keto oxime.
제조예 1-1: 화합물 1의 합성Preparation Example 1-1: Synthesis of Compound 1
500ml 4-neck 둥근바닥 플라스크에 Nitrobenzene(TCI사) 10g, dichloro ethane 200g을 순차적으로 투입한 후 10℃이하에서 AlCl3 12.02g을 투입하였다. 냉각을 유지하면서 Otanoyl chloride 15.0g을 천천히 투입한 다음 실온으로 온도를 올려 일야 교반을 실시하였다. 반응이 완료된 후 Methylene chloride/H2O를 이용하여 추출을 진행한하고, 이후 유기층을 수집 농축하여 순도 93%, 수율 80%의 노란색의 고체 화합물을 수득하였다.Into a 500 ml 4-neck round-bottom flask, 10 g of Nitrobenzene (TCI) and 200 g of dichloro ethane were sequentially added, followed by 12.02 g of AlCl 3 at 10°C or lower. While maintaining the cooling, 15.0 g of Otanoyl chloride was slowly added, and then the temperature was raised to room temperature to perform stirring overnight. After the reaction was completed, extraction was performed using Methylene chloride/H 2 O, and then the organic layer was collected and concentrated to obtain a yellow solid compound having a purity of 93% and a yield of 80%.
Friedel Craft reactionFriedel Craft reaction
상기 과정에서 합성한 1-(3-nitrophenyl)octan-1-one 15g을 THF 200g에 투입한 후 10℃이하에서 Isoamyl nitrite 8.53g을 투입하였다. HCl gas를 30분간 0.5L 투입하고, 10℃에서 일야 교반을 실시하였다. 반응이 완료된 후 Methylene chloride/H2O를 이용하여 추출을 진행하고, 이후 유기층을 진공농축하여 수득된 적갈색 점성체를 ethyl acetate/n-hexane가 2:1의 비율로 혼합된 전개액을 이용하여 실리카겔 컬럼크로마토그래피를 통하여 정제함으로써, 순도 99%, 수율 70%의 화학식 1-1로 표시되는 화합물을 수득하였다.15 g of 1-(3-nitrophenyl)octan-1-one synthesized in the above process was added to 200 g of THF, and 8.53 g of Isoamyl nitrite was added at 10°C or less. HCl gas was added for 0.5L for 30 minutes, and stirring was performed at 10°C overnight. After the reaction was completed, extraction was carried out using Methylene chloride/H 2 O, and then the red brown viscous body obtained by vacuum concentration of the organic layer was used with a developing solution in which ethyl acetate/n-hexane was mixed at a ratio of 2:1. Purification through silica gel column chromatography gave a compound represented by Formula 1-1 with a purity of 99% and a yield of 70%.
OximationOximation
제조예 1-2, 1-3: 화합물 2, 3의 합성Preparation Examples 1-2, 1-3: Synthesis of Compound 2, 3
Nitrobenzene 대신 Benzophenone / Nitrobenzophenone을 사용한 것을 제외하고는 제조예 1-1과 동일한 방법으로 화학식 1-2 및 화학식 1-3으로 표시되는 화합물을 각각 수득하였다.Compounds represented by Chemical Formulas 1-2 and 1-3 were obtained in the same manner as in Production Example 1-1, except that Benzophenone / Nitrobenzophenone was used instead of Nitrobenzene.
제조예 1-4: 화합물 4의 합성Preparation Example 1-4: Synthesis of Compound 4
500ml 4-neck 둥근바닥 플라스크에 N-ethylcarbazole 30g, Methylene chloride 240g을 순차적으로 투입하여 용해 냉각한 후 10℃이하에서 AlCl3 24.31g을 투입하였다. 반응액의 온도를 5℃ 이하로 유지하면서 o-Toluoyl chloride 24.22g을 천천히 적가한 다음 반응이 완료된 후 AlCl3 22.35g 및 Propionyl chloride 14.9g를 순차적으로 천천히 투입한 후에 온도를 실온으로 승온하여 일야 교반하였다. 반응 완료된 후 Methylene chloride/H2O를 이용하여 추출을 진행하고, 이후 유기층을 수집 농축한 다음 MeOH를 이용하여 재결정을 실시하여 순도 98%, 수율 62%의 노란색의 고체화합물을 수득하였다.In a 500 ml 4-neck round-bottom flask, 30 g of N-ethylcarbazole and 240 g of Methylene chloride were sequentially added to dissolve and cool, followed by 24.31 g of AlCl 3 at 10°C or lower. While maintaining the temperature of the reaction solution at 5° C. or less, 24.22 g of o-Toluoyl chloride was slowly added dropwise, and after the reaction was completed, 22.35 g of AlCl 3 and 14.9 g of Propionyl chloride were slowly added sequentially, and the temperature was raised to room temperature and stirred overnight. Did. After the reaction was completed, extraction was performed using Methylene chloride/H 2 O, and then, the organic layer was collected and concentrated, and then recrystallized using MeOH to obtain a yellow solid compound having a purity of 98% and a yield of 62%.
이하 oximation은 제조예 1-1의 합성법과 동일한 방법으로 화학식 1-4로 표시되는 화합물을 수득하였다.Hereinafter, oximation was obtained in the same manner as in the synthesis method of Preparation Example 1-1 to obtain a compound represented by Formula 1-4.
제조예 1-5: 화합물 5의 합성Preparation Example 1-5: Synthesis of Compound 5
제조예 1-4에서 o-Toluoyl chloride 대신에 2-thiophenecarboxylic chloride를 사용한 것을 제외하고는 동일한 방법으로 화학식 1-5로 표시되는 화합물을 수득하였다.In Preparation Example 1-4, a compound represented by Chemical Formula 1-5 was obtained in the same manner, except that 2-thiophenecarboxylic chloride was used instead of o-Toluoyl chloride.
제조예 1-6: 화합물 6의 합성Preparation Example 1-6: Synthesis of Compound 6
500ml 4-neck 둥근바닥 플라스크에 N-ethyl-carbazole(TCI사) 100g, dichloro ethane 200g을 순차적으로 투입하여 용해 냉각한 후 10℃이하에서 70% HNO3 42g을 천천히 투입하였다. 반응액의 온도를 10℃이하로 유지하며, 반응 완료된 후 Methylene chloride/H2O를 이용하여 추출을 진행하였다. 이후 유기층을 수집 농축하여 얻은 적갈색 점성체를 ethyl acetate/n-hexane가 1:1의 비율로 혼합된 전개액을 이용하여 실리카겔 컬럼크로마토그래피를 통하여 정제함으로써, 순도 96%, 수율 76%의 화합물을 수득하였다.Into a 500 ml 4-neck round-bottom flask, 100 g of N-ethyl-carbazole (TCI) and 200 g of dichloro ethane were sequentially added to dissolve and cool, and then 42 g of 70% HNO 3 was slowly added at 10° C. or less. The temperature of the reaction solution was maintained below 10°C, and after the reaction was completed, extraction was performed using Methylene chloride/H 2 O. Thereafter, the reddish-brown viscous material obtained by collecting and concentrating the organic layer was purified by silica gel column chromatography using a developing solution in which ethyl acetate/n-hexane was mixed at a ratio of 1:1 to obtain a compound having a purity of 96% and a yield of 76%. Obtained.
NitrationNitration
이하 oximation은 제조예 1-1의 합성법과 동일한 방법으로 화학식 1-6으로 표시되는 화합물을 수득하였다.Hereinafter, oximation was obtained in the same manner as in the synthesis method of Preparation Example 1-1 to obtain a compound represented by Formula 1-6.
제조예 1-7~1-21: 화합물 7~21의 합성Preparation Examples 1-7 to 1-21: Synthesis of Compounds 7 to 21
제조예 1-1~1-6에 기재한 합성법과 동일한 방법으로, 화학식 1-7 내지 1-21로 표시되는 화합물을 각각 수득하였다.In the same manner as the synthesis method described in Production Examples 1-1 to 1-6, compounds represented by Chemical Formulas 1-7 to 1-21 were obtained, respectively.
제조예 2-1 내지 제조예 2-5. 분산액 제조Production Example 2-1 to Production Example 2-5. Dispersion preparation
하기 표 2에 개시된 조성 비율로 각각 혼합하여 제조예 2-1 내지 제조예 2-5의 분산액을 제조하였다.Dispersions of Preparation Examples 2-1 to 2-5 were prepared by mixing at the composition ratios shown in Table 2 below.
우선, 페녹시에틸아크릴레이트 80중량%에 분산염료 15중량%, 분산제 5중량%를 혼합한 후 고속교반기를 이용하여 2시간 교반한 다음 0.3mm 지르코니아 비드로 3시간 교반하여 제조예 2-1 내지 제조예 2-5의 분산액을 제조하였다.First, after mixing 15% by weight of a disperse dye and 5% by weight of a dispersant in 80% by weight of phenoxyethyl acrylate, and then stirring for 2 hours using a high-speed stirrer, followed by stirring for 3 hours with 0.3mm zirconia beads to prepare Examples 2-1 to The dispersion of Preparation Example 2-5 was prepared.
표 2는 분산액의 혼합 중량%를 나타낸 도이다.Table 2 is a diagram showing the mixed weight percent of the dispersion.
(Yellow 150)Yellow
(Yellow 150)
(Blue 15:4)Cyan
(Blue 15:4)
실시예 1 내지 실시예 12. 광경화형 잉크의 제조Examples 1 to 12. Preparation of photocurable ink
하기 표 3, 표 4에 개시된 조성비율로 각각 혼합하여 실시예 1 내지 실시예 12와 비교예 1, 2의 잉크를 제조하였다. Inks of Examples 1 to 12 and Comparative Examples 1 and 2 were prepared by mixing at the composition ratios shown in Tables 3 and 4, respectively.
우선, 반응 용기에 페녹시 에틸아크릴레이트(PEA), 이소보닐아크릴레이트(IBOA), 테트라하이드로퍼퓨릴(THFA), N-비닐카프로락탐(NVC) 를 투입하고 30분간 교반하였다. 그리고, 광중합 개시제, 디페닐(2,4,6-(트리메틸벤조일))포스핀 옥사이드(TPO), 폴리디메틸실록산, 트리메틸롤프로판 -트리아크릴레이트(TMOTA), 광증감제(NeoRad U-70(Agi사 Mw=800)), 및 분산액을 순차적으로 투입하여 교반 용해한 후 Microfilter(5um)를 통하여 점도 21.1cps (at 35℃), 표면장력 34mN/m인 실시예 1 내지 실시예 12의 잉크를 제조하였다.First, phenoxy ethyl acrylate (PEA), isobornyl acrylate (IBOA), tetrahydrofurfuryl (THFA) and N-vinyl caprolactam (NVC) were added to the reaction vessel and stirred for 30 minutes. And, photopolymerization initiator, diphenyl (2,4,6-(trimethylbenzoyl)) phosphine oxide (TPO), polydimethylsiloxane, trimethylolpropane-triacrylate (TMOTA), photosensitizer (NeoRad U-70 ( Agi Mw = 800)), and the dispersion was sequentially added and dissolved by stirring to prepare the inks of Examples 1 to 12 having a viscosity of 21.1 cps (at 35°C) and a surface tension of 34 mN/m through a Microfilter (5 um). Did.
하기 표 4에 개시된 조성비율로 각각 혼합한 것을 제외하고는 실시예 1 내지 실시예 12의 제조방법과 동일한 방법으로 비교예 1, 2의 잉크를 제조하였다.Inks of Comparative Examples 1 and 2 were prepared in the same manner as in the production method of Examples 1 to 12, except that each was mixed at the composition ratios disclosed in Table 4 below.
표 3 및 표 4는 잉크의 혼합 중량%를 나타낸 표이다. Tables 3 and 4 are tables showing the mixed weight% of the ink.
실험예 1. 물리적 특성Experimental Example 1. Physical properties
본 발명에 따른 실시예 1 내지 실시예 12 및 비교예 1, 2의 물리적 특성을 하기의 방법으로 각각 측정하였다. The physical properties of Examples 1 to 12 and Comparative Examples 1 and 2 according to the present invention were respectively measured by the following methods.
광경화 잉크들을 미마키사의 UJF-6042 MK II 장비를 이용하여 하기 표 5의 출력조건으로 출력평가를 하였고, 경화테스트는 385nm영역의 LED-UV lamp를 가진 미마키사의 UJF-6042 MK II 제품을 사용하여 실시하였다. The photo-curing inks were evaluated for output using the MJ-Uki UJF-6042 MK II equipment under the output conditions shown in Table 5 below, and the curing test was performed using a MJ-Uki UJF-6042 MK II product with a 385nm LED-UV lamp. It was carried out using.
[경화도][Hardening degree]
경화도는 출력이 완료된 후 경화물을 따로 수집하여 IR spectroscopy를 측정하여 불포화결합이 없어진 정도를 하기 식(1) 또는 식(2)을 이용하여 계산한 후 이를 식(3)에 적용하여 변환율을 계산하였다. 변환율이 높을수록 경화가 많이 되었다고 판단할 수 있다. After the output is completed, the cured product is collected separately, IR spectroscopy is measured, and the degree of unsaturated bond disappearance is calculated using the following equation (1) or equation (2), and then applied to equation (3) to calculate the conversion rate. Did. It can be determined that the higher the conversion rate, the more the hardening.
Ratio(A)=경화전 조성물 C=C peak적분값/경화전 조성물 C=O peak 적분값.......식(1)Ratio(A)=Pre-curing composition C=C peak integral value/Pre-curing composition C=O peak integral value....(1)
Ratio(B)=경화후 조성물 C=C peak적분값/경화후 조성물 C=O peak 적분값.......식(2)Ratio(B)=C=C peak integration value after curing/C=O peak integration value after curing C...O(2)
변환율(%)=100-(Ratio(A)/Ratio(B))......식(3)Conversion rate (%)=100-(Ratio(A)/Ratio(B))......Equation (3)
[부착성] [Adhesiveness]
부착성은 광경화 조성물이 프린팅되는 기재에 부착되는 정도를 평가하는 것으로, 1mm 간격으로 10X10 cutting 후, 테이프를 완전 밀착 시켰다 떼어내어 도막이 떨어진 정도로 표 6을 참조하여 등급을 판단하였다.Adhesion is to evaluate the degree to which the photocurable composition adheres to the printed substrate, and after 10X10 cutting at 1 mm intervals, the tape is completely adhered and peeled off.
[경도][Hardness]
경화된 인쇄물의 내스크레치성을 평가하고자 함이며, 그 측정방법은 시험판 위에 750g 하중의 연필 시험기를 올리고 시험기에 연필을 45°각도로 고정한 후 작업자 반대 방향으로 밀어주었다.The purpose of this study is to evaluate the scratch resistance of the cured print, and the measuring method is to put a pencil tester with a load of 750g on a test plate, fix the pencil at a 45° angle to the tester, and push it in the opposite direction of the worker.
- 결과 분류: 시험판에 흠집을 남기지 않는 최대의 연필 경도로 등급을 매긴다(연필 경도: 6B, 5B, 4B, 3B, 2B, B, HB, H, 2H, 3H, 4H, 5H, 6H / 연필 경도가 높을수록 경도가 좋다고 판단).-Classification of results: Graded with maximum pencil hardness that does not scratch the test panel (pencil hardness: 6B, 5B, 4B, 3B, 2B, B, HB, H, 2H, 3H, 4H, 5H, 6H / pencil hardness It is judged that the higher is, the better the hardness).
[평가결과] [Evaluation results]
평가결과는 하기 표 7과 같다. The evaluation results are shown in Table 7 below.
그 결과, 표 7을 참조하면, 본 발명의 옥시 화합물을 함유하는 광중합 개시제가 포함된 실시예 1 내지 실시예 12는 일반적인 광중합 개시제를 포함하는 비교예 1, 2에 비해 경도, 부착성, 경화도, 색상도 전반에 걸쳐 우수한 특성을 나타냄을 확인할 수 있었다.As a result, referring to Table 7, Examples 1 to 12 in which the photopolymerization initiator containing the oxy compound of the present invention was included was compared with Comparative Examples 1 and 2 containing the general photopolymerization initiator in hardness, adhesion, and curing degree. , It was confirmed that the color also showed excellent properties throughout.
이상 본 발명자에 의해서 이루어진 발명을 상기 실시예에 따라 구체적으로 설명하였지만, 본 발명은 상기 실시예에 한정되는 것은 아니고 그 요지를 이탈하지 않는 범위에서 여러가지로 변경 가능한 것은 물론이다.Although the invention made by the present inventors has been described in detail according to the above-described embodiments, the present invention is not limited to the above-described embodiments and can be variously changed without departing from the gist thereof.
Claims (10)
[화학식 1]
상기 화학식 1에서,
R1은 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬 또는 비치환의 C6-C20 알릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬로 이루어진 군으로부터 선택되고,
R2 내지 R6는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C6-C20 아릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬, 할로겐, CN, NO2, NR7R8, SR9, COOR10, COR11, SO2R12으로 이루어진 군으로부터 선택되고, 여기서, 헤테로 원자는 N, O 및 S로 이루어진 군으로부터 선택되며, R7 내지 R12는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄 또는 측쇄 알킬, 및 치환 또는 비치환의 C6-C20 아릴로 이루어진 군으로부터 선택된다.
Photopolymerization initiator comprising an oxime compound represented by the following formula (1).
[Formula 1]
In Chemical Formula 1,
R 1 is substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl or unsubstituted C 6 -C 20 allyl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl,
R 2 to R 6 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, halogen, CN, NO 2 , NR 7 R 8 , SR 9 , COOR 10 , COR 11 , SO 2 R 12 Wherein, the hetero atom is selected from the group consisting of N, O and S, R 7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain or branched alkyl, and substituted or unsubstituted C 6 -C 20 aryl.
[화학식 2]
상기 화학식 2에서,
R1은 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬 또는 비치환의 C6-C20 알릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬로 이루어진 군으로부터 선택되고,
R2, R5, R6 및 R13 내지 R16는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알케닐, 치환 또는 비치환의 C1-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C6-C20 아릴, 치환 또는 비치환의 C3-C20 (헤테로) 시클로 알킬, 할로겐, CN, NO2, NR7R8, SR9, COOR10, COR11, SO2R12으로 이루어진 군으로부터 선택되고, 여기서, 헤테로 원자는 N, O 및 S로 이루어진 군으로부터 선택되며, R7 내지 R12는 각각 독립적으로 수소, 치환 또는 비치환의 C1-C20 직쇄 또는 측쇄 알킬, 및 치환 또는 비치환의 C6-C20 아릴로 이루어진 군으로부터 선택되고,
R17은 치환 또는 비치환의 C4-C20 직쇄, 측쇄 또는 환상 알킬, 치환 또는 비치환의 C4-C20 직쇄 또는 측쇄 알콕시알킬기, 및 치환 또는 비치환의 C6-C20 아릴, 및 치환 또는 비치환의 C7-C20 아릴알킬로 이루어진 군으로부터 선택되며,
A는 C, N, O, S 원소로 이루어진 군으로부터 선택된다.
Photopolymerization initiator comprising an oxime compound represented by the following formula (2).
[Formula 2]
In Chemical Formula 2,
R 1 is substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkyl or unsubstituted C 6 -C 20 allyl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl,
R 2 , R 5 , R 6 and R 13 to R 16 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain, branched or cyclic alkenyl, substituted or unsubstituted C 1 -C 20 straight chain, side chain or Cyclic alkyl, substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 3 -C 20 (hetero) cycloalkyl, halogen, CN, NO 2 , NR 7 R 8 , SR 9 , COOR 10 , COR 11 , SO 2 R 12 is selected from the group consisting of, wherein the hetero atom is selected from the group consisting of N, O and S, R 7 to R 12 are each independently hydrogen, substituted or unsubstituted C 1 -C 20 straight chain or Branched alkyl, and substituted or unsubstituted C 6 -C 20 aryl,
R 17 is a substituted or unsubstituted C 4 -C 20 straight chain, branched or cyclic alkyl, substituted or unsubstituted C 4 -C 20 straight chain or branched alkoxyalkyl group, and Selected from the group consisting of substituted or unsubstituted C 6 -C 20 aryl, and substituted or unsubstituted C 7 -C 20 arylalkyl,
A is selected from the group consisting of C, N, O, and S elements.
상기 옥심 화합물은
The method according to claim 1 or 2,
The oxime compound
A photocurable ink composition comprising a photopolymerization initiator comprising the oxime compound of claim 1.
상기 조성물은
광중합 개시제 1~20중량%;
에틸렌계 불포화 결합을 가지는 화합물 40~90중량%;
에틸렌 불포화 결합을 다관능으로 가지는 화합물 5~30중량%;
분산액 5~15중량%; 및
분산제, 광증감제 및 이들의 조합으로부터 선택되는 첨가제 0.01~5중량%를 포함하는 광경화형 잉크 조성물.
According to claim 4,
The composition
1-20% by weight of a photopolymerization initiator;
40 to 90% by weight of a compound having an ethylenically unsaturated bond;
5 to 30% by weight of a compound having a polyfunctional ethylenically unsaturated bond;
Dispersion 5 to 15% by weight; And
Photocurable ink composition comprising 0.01 to 5% by weight of additives selected from dispersants, photosensitizers and combinations thereof.
상기 광중합 개시제는 벤질, 벤조인에테르, 벤조인 부틸에테르, 벤조인프로필에테르, 벤조페논, 3'-디메틸-4-메톡시벤조페논, 벤조일벤조산, 벤조일벤조산의 에스테르화물, 4-벤조일-4'-메틸디페닐설파이드, 벤질 디메틸케탈, 2-부톡시에틸-4-메틸아미노벤조에이트, 클로로티옥산톤, 메틸티옥산톤, 에틸티옥산톤, 이소프로필티옥산톤, 디메틸티옥산톤, 디에틸티옥산톤, 디이소프로필티옥산톤, 디메틸아미노메틸벤조에이트, 디메틸아미노벤조산 이소아밀에스테르, 1- (4-도데실페닐)-2-하이드록시-2-메틸프로판-1-온, 1-하이드록시사이클로헥실페닐 케톤, 2-하이드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-하이드록시-2-메틸프로판-1-온, 메틸벤조일포름에이트, 2-메틸-1- (4-메틸티오페닐) -2-모폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모폴리노페닐)-부탄-1-온, 2.2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비스이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라-(4-메톡시페닐)비스이미다졸, 디페닐(2,4,6-(트리메틸벤조일))포스핀 옥사이드, 페닐비스(2,4,6-트리메틸벤조일)포스핀 옥사이드 및 이들의 조합으로부터 선택되는 1종을 더 포함하는 광경화형 잉크 조성물.
The method of claim 4 or 5,
The photopolymerization initiator is benzyl, benzoin ether, benzoin butyl ether, benzoinpropyl ether, benzophenone, 3'-dimethyl-4-methoxybenzophenone, benzoylbenzoic acid, esterified product of benzoylbenzoic acid, 4-benzoyl-4' -Methyldiphenylsulfide, benzyl dimethyl ketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dimethylthioxanthone, di Ethyl thioxanthone, diisopropyl thioxanthone, dimethylaminomethylbenzoate, dimethylaminobenzoic acid isoamyl ester, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, Methylbenzoylformate, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- Butan-1-one, 2.2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra-(4-methoxyphenyl)bisimidazole, diphenyl(2,4,6-(trimethylbenzoyl))phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phos A photocurable ink composition further comprising one selected from pin oxide and combinations thereof.
상기 에틸렌계 불포화 결합을 가지는 화합물은 아크릴산, 메타아크릴산, 아크릴산 에스테르, 메타크릴산 에스테르, 스틸렌, 아크릴로니트릴 및 이들의 조합으로부터 선택되는 1종인 광경화형 잉크 조성물.
The method of claim 5,
The compound having an ethylenically unsaturated bond is one type selected from acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene, acrylonitrile, and combinations thereof.
상기 에틸렌 불포화 결합을 다관능으로 가지는 화합물은 디펜타에리스리톨 아크릴레이트, 글리세롤 트리아크릴레이트, 펜타에리스리톨 트리테트라아크릴레이트, 트리메틸롤프로판에톡시 트리아크릴레이트, 트리메틸롤프로판 트리아크릴레이트, 디트리메틸롤프로판 테트라아크릴레이트 및 이들의 조합으로부터 선택되는 1종인 광경화형 잉크 조성물.
The method of claim 5,
The compound having a polyfunctional ethylenically unsaturated bond is dipentaerythritol acrylate, glycerol triacrylate, pentaerythritol tritetraacrylate, trimethylolpropaneethoxy triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetra Photocurable ink composition, which is one type selected from acrylates and combinations thereof.
상기 분산액은
용제 70~90중량%;
분산염료 1~20중량%; 및
분산제 1~10중량%를 포함하는 광경화형 잉크 조성물.
The method of claim 5,
The dispersion is
Solvent 70-90% by weight;
Disperse dye 1-20% by weight; And
A photocurable ink composition comprising 1-10% by weight of dispersant.
상기 분산제는 음이온성 계면활성제, 비이온성 계면활성제, 양쪽성 계면활성제, 고분자계 분산제 및 이들의 조합으로부터 선택되는 1종인 광경화형 잉크 조성물.The method of claim 9,
The dispersant is a photocurable ink composition that is one type selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, polymer-based dispersants and combinations thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020180168371A KR102125820B1 (en) | 2018-12-24 | 2018-12-24 | Photopolymerization initiator comprising oxime compounds and photocurable electroductive ink composition having the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020180168371A KR102125820B1 (en) | 2018-12-24 | 2018-12-24 | Photopolymerization initiator comprising oxime compounds and photocurable electroductive ink composition having the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR102125820B1 true KR102125820B1 (en) | 2020-06-23 |
Family
ID=71137820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020180168371A KR102125820B1 (en) | 2018-12-24 | 2018-12-24 | Photopolymerization initiator comprising oxime compounds and photocurable electroductive ink composition having the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102125820B1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060049359A (en) | 2004-11-12 | 2006-05-18 | 가부시키가이샤 니콘 | Driving apparatus and exposure apparatus |
| KR100633044B1 (en) | 2004-07-26 | 2006-10-12 | 한국기계연구원 | Sliding construction of hydraulic power pump |
| JP2006351995A (en) | 2005-06-20 | 2006-12-28 | Sharp Corp | Manufacturing method of photoelectric conversion device |
| KR100801457B1 (en) | 2001-06-11 | 2008-02-11 | 시바 스페셜티 케미칼스 홀딩 인크. | Oxime ester photoinitiators having a combined structure |
| KR20090104877A (en) * | 2007-01-23 | 2009-10-06 | 후지필름 가부시키가이샤 | Oxime compound, photosensitive composition, color filter, method for production of the color filter, and liquid crystal display element |
| JP2010215575A (en) * | 2009-03-18 | 2010-09-30 | Toyo Ink Mfg Co Ltd | New oxime ester compound, radical polymerization initiator containing the same, polymerizable composition, negative type resist by using the same and method for forming image pattern by using the same |
| JP2013249269A (en) * | 2012-05-30 | 2013-12-12 | Mitsubishi Chemicals Corp | Ketoxime ester compound, curable resin composition, cured product, interlayer dielectric film, tet active matrix substrate, and liquid crystal display device |
-
2018
- 2018-12-24 KR KR1020180168371A patent/KR102125820B1/en active IP Right Grant
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100801457B1 (en) | 2001-06-11 | 2008-02-11 | 시바 스페셜티 케미칼스 홀딩 인크. | Oxime ester photoinitiators having a combined structure |
| KR100633044B1 (en) | 2004-07-26 | 2006-10-12 | 한국기계연구원 | Sliding construction of hydraulic power pump |
| KR20060049359A (en) | 2004-11-12 | 2006-05-18 | 가부시키가이샤 니콘 | Driving apparatus and exposure apparatus |
| JP2006351995A (en) | 2005-06-20 | 2006-12-28 | Sharp Corp | Manufacturing method of photoelectric conversion device |
| KR20090104877A (en) * | 2007-01-23 | 2009-10-06 | 후지필름 가부시키가이샤 | Oxime compound, photosensitive composition, color filter, method for production of the color filter, and liquid crystal display element |
| JP2010215575A (en) * | 2009-03-18 | 2010-09-30 | Toyo Ink Mfg Co Ltd | New oxime ester compound, radical polymerization initiator containing the same, polymerizable composition, negative type resist by using the same and method for forming image pattern by using the same |
| JP2013249269A (en) * | 2012-05-30 | 2013-12-12 | Mitsubishi Chemicals Corp | Ketoxime ester compound, curable resin composition, cured product, interlayer dielectric film, tet active matrix substrate, and liquid crystal display device |
Non-Patent Citations (1)
| Title |
|---|
| Progress in Organic Coatings 58, 146, 2007 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI724087B (en) | Photocurable inkjet printing ink composition and inkjet printing method | |
| CN103073945B (en) | Active energy ray-curable ink-jet magenta ink composition | |
| CN1964997B (en) | Radiation-curable high gloss overprint varnish compositions | |
| EP3263655B1 (en) | Ink composition for photocurable inkjet printing | |
| JP6011744B2 (en) | COMPOUND, ACTIVE ENERGY RAY CURABLE COMPOSITION, CURED PRODUCT, PRINTING INK AND INKJET RECORDING INK | |
| JP2012031254A (en) | Uv-curable inkjet ink composition | |
| CN104249579A (en) | Ink jet recording method | |
| JP5939114B2 (en) | Active energy ray-curable inkjet ink composition | |
| JP2008120991A (en) | Two-pack photocurable ink set | |
| JP6445240B2 (en) | Photocurable ink composition for ink jet printing and ink jet recording method | |
| WO2010058816A1 (en) | Energy beam-curing inkjet ink composition | |
| JP2017095531A (en) | Ink composition for photosetting inkjet printing | |
| JP2005178331A (en) | Ink and method for inkjet recording | |
| JP2018131535A (en) | Photocurable inkjet ink | |
| JP5621251B2 (en) | UV curable inkjet ink and printed matter | |
| KR102125820B1 (en) | Photopolymerization initiator comprising oxime compounds and photocurable electroductive ink composition having the same | |
| JP5545533B2 (en) | Radical photocurable ink composition | |
| JP2022524145A (en) | Curable ink composition | |
| JP2008195913A (en) | Photocuring ink composition set, recording method using the ink composition set and recorded matter | |
| JP2011201932A (en) | Ink composition, inkjet recording method, and printed matter | |
| WO2011158593A1 (en) | Photocurable ink jet ink, method for forming image, maleimide derivative and photocurable composition | |
| JP6127905B2 (en) | Active energy ray curable inkjet ink set | |
| WO2013031870A1 (en) | Active energy ray-curable inkjet magenta ink composition | |
| JP5704797B2 (en) | Method for producing energy ray curable inkjet ink composition | |
| JP5979280B2 (en) | Radical photocurable ink composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |