WO2010028844A1 - Light curing compositions - Google Patents
Light curing compositions Download PDFInfo
- Publication number
- WO2010028844A1 WO2010028844A1 PCT/EP2009/006617 EP2009006617W WO2010028844A1 WO 2010028844 A1 WO2010028844 A1 WO 2010028844A1 EP 2009006617 W EP2009006617 W EP 2009006617W WO 2010028844 A1 WO2010028844 A1 WO 2010028844A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- formula
- aryl
- heteroaryl
- substituent
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 230000003287 optical effect Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 36
- 125000003118 aryl group Chemical group 0.000 claims description 21
- -1 C 1 -C 4 alkyl Chemical group 0.000 claims description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 16
- 125000004442 acylamino group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000004423 acyloxy group Chemical group 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000004001 thioalkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- LOTBYPQQWICYBB-UHFFFAOYSA-N methyl n-hexyl-n-[2-(hexylamino)ethyl]carbamate Chemical compound CCCCCCNCCN(C(=O)OC)CCCCCC LOTBYPQQWICYBB-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 5
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000005548 dental material Substances 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 150000007824 aliphatic compounds Chemical class 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 150000002390 heteroarenes Chemical group 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000000206 photolithography Methods 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims 1
- 239000004922 lacquer Substances 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 4
- 239000000049 pigment Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 5
- SUAMDPNSQBFZHW-UHFFFAOYSA-N 3-hydroxy-1-sulfanylidene-2h-1,3-thiazole Chemical compound ON1CS(=S)C=C1 SUAMDPNSQBFZHW-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 241000894007 species Species 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 125000001589 carboacyl group Chemical group 0.000 description 4
- 150000002790 naphthalenes Chemical group 0.000 description 4
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000010546 Norrish type I reaction Methods 0.000 description 3
- 238000010547 Norrish type II reaction Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- CARNFEUGBMWTON-UHFFFAOYSA-N 3-(2-prop-2-enoxyethoxy)prop-1-ene Chemical compound C=CCOCCOCC=C CARNFEUGBMWTON-UHFFFAOYSA-N 0.000 description 1
- GJZGXOJVFPHTGC-UHFFFAOYSA-N 4-amino-1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(N)C(=O)C(=O)C1(C)C2(C)C GJZGXOJVFPHTGC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- IXNDUSYZJBQPJN-UHFFFAOYSA-N C(=O)(C=C)[PH2]=O Chemical class C(=O)(C=C)[PH2]=O IXNDUSYZJBQPJN-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 0 O=C(*C(Cl)=O)Cl Chemical compound O=C(*C(Cl)=O)Cl 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XVHANQPWGFCVMF-UHFFFAOYSA-N [5-(4-methoxyphenyl)-4-methyl-2-sulfanylidene-1,3-thiazol-3-yl] benzoate Chemical compound C1=CC(OC)=CC=C1C1=C(C)N(OC(=O)C=2C=CC=CC=2)C(=S)S1 XVHANQPWGFCVMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000313 dental photoinitiator Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- YNRKXBSUORGBIU-UHFFFAOYSA-N hydroxycarbamothioic s-acid Chemical compound ONC(S)=O YNRKXBSUORGBIU-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical group OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000002023 wood Substances 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/84—Sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/36—Sulfur atoms
Definitions
- the present invention relates to light-curable or photocurable compositions comprising radically polymerizable compounds, in particular vinyl compounds and daylight-sensitive radical initiators and optionally further additives such as fillers, pigments, solvents, and their use as coating material for technical, optical and medical applications. Moreover, the invention relates to cured products prepared from the compositions, including their methods of preparation. Finally, the invention also relates to the novel compounds used as radical initiators as such and to a process for their preparation.
- Photoinitiators absorb radiation in the UV or in the visual range, thus providing polymerization-initiating species.
- radical photoinitiators radiation initiators
- Norrish Type I photoinitiators form free radicals due to unimolecular bond breaking radiation.
- Norrish Type II photoinitiators undergo a bimolecular reaction upon exposure to radiation, with the photoinitiator reacting with a second molecule (the coinitiator) and forming the polymerization initiating species by electron and proton transfer or directly by hydrogen abstraction.
- Norrish type I and II photoinitiators are used in curing with UV light.
- Norrish type II photoinitiators are used for polymerization by irradiation with visual light.
- Characteristic of the curing by radiation in the UV range is the high reaction rate.
- This type of curing is used for example for coatings of various substrates such as wood.
- Such an example of UV-curable coatings of materials with Norrish Type I photoinitiators, such as diethoxyphenylacetophenone or acrylic phosphine oxides, is disclosed in U.S. Pat EP 1247843.
- WO 01/51533 describes a UV-curable wood-plating material using acrylphosphine oxides, ⁇ -hydroxyalkylphenones or ⁇ -dialkoxyacetophenones as photoinitiators.
- UV curing can be used for all transparent coatings with low layer thicknesses. However, it reaches its limits with an admixture of pigments and at higher layer thicknesses. Such photopoly-reactive compounds therefore cure only incompletely by UV radiation. If a deeper through cure is desired, such as in the photohardening of dental materials to be used as a dental filling, visible light may be used for irradiation which has a higher penetrating power.
- a photoinitiator that can be used for such purposes is a combination of ⁇ -diketones and amino coinitiators. Such a system is described in GB 1, 408,265.
- the initiator systems known in the prior art are not capable of ensuring sufficiently rapid and complete curing of the desired materials in each case. Rather, the known compounds which provide by means of short-wave light (UV range) polymerization initializing species available, the disadvantage that the short-wave radiation achieves only a small penetration depth. This is particularly problematic when used in systems with fillers. Moreover, no systems were available that readily provide polymerization initiating species by means of visible light (daylight) and without coinitiators. Thus, there was still an urgent need to divide up new ones simple yet powerful initiators that can be efficiently activated by visible light.
- UV range ultraviolet range
- novel photoinitiators for radical polymerization are represented by formulas (I) and (II) wherein the compounds of formula (I) are the monomers and those of formula (II) are the dimeric structures ,
- the dimeric structures have approximately the same efficiency in the initiator effect, but also have a lower diffusibility, which may be of practical relevance.
- X S, CHR 4 , O, or NR 4 ;
- R 1 and R 2 are each independently H, linear or branched C 1 -C 20
- R 3 H, linear or branched C 1 -C 20 -alkyl; thioalkyl; aryl; Heteroaryl is;
- R 4 H, linear or branched C 1 -C 20 -alkyl, where the alkyl substituent may have cyclic substructures; acyloxy; aryl; or heteroaryl;
- A is an aliphatic, aromatic or heteroaromatic compound group.
- the polymerization initiators according to formula (I) or (II) according to the invention are used in light-curing or photocurable composition. These compositions comprise: a. at least one radically polymerizable compound, in particular vinyl compound; and b. at least one compound of formula (I) and / or formula (II) as a radical initiator.
- the invention further relates to the cured product obtainable by photohardening this composition with visible light, and to the photohardening process for producing such a cured product as such.
- the invention relates in particular to the use of the compounds of the formula (I) and / or of the formula (II) as radical initiator for free-radical polymerization.
- the invention also relates to a novel preparation process for the compounds of the formula (I) and / or of the formula (II).
- R 3 may be a heteroaromatic radical, wherein the term heteroaroamtisch preferably refers to pyridine, pyrrole, thiophene and furan and derivatives thereof.
- Formula (I) is exemplified below. CHR 4 , O, NR 4 preferably S
- A is preferably a pyridine, pyrrole, thiophene, furan, thiazole, oxazole or imidazole group or a derivative thereof or a monosubstituted to tetra-substituted or unsubstituted phenylene group.
- R 1 , R 2 , R 3 and R 4 are preferably independently of one another H, C 1 -C 20 -alkyl, aryl or heteroaryl; where aryl is a monosubstituted to trisubstituted phenyl substituent or a monosubstituted to trisubstituted naphthalene substituent, the substituents being selected from halogen, in particular chlorine, C 1 -C 10 -alkoxy, C 1 -C 20 -alkyl, aminoalkyl, C 1 -C 10 -alkyl, Mono- or dialkylamino, acylamino, nitro, cyano, alkoxycarbonyl; and heteroaryl is substituted or unsubstituted pyridine, pyrrole, thiophene or furan.
- A is preferably a pyridine, pyrrole, thiophene, furan, thiazole, oxazole or imidazole group or a derivative thereof, or a mono- to tetra-substituted or unsubstituted phenylene group.
- the definition of the substituents on the phenylene group corresponds to the definition given above.
- R 2 in formula (I) or (II) is particularly preferably not H 1 because in these compounds (ie in which R 2 is C 1 -C 20 -alkyl, aryl or heteroaryl as defined above) a surprisingly higher sensitivity in the visible range of Light occurs.
- the reason for this is assumed to be a bathochromic shift of the longest-wavelength absorption maximum of the chromophore (eg of the thiazole-2 (3H) chromophore) in the case of alkyl and in particular aryl substituents R 2 and an associated higher sensitivity in the visible range.
- the chromophore eg of the thiazole-2 (3H) chromophore
- Unsaturated cyclics formed by R 1 and R 2 are especially phenyl, indene, coumarone (benzofuran), indole, thionaphthene (benzothiophene), naphthalene which may be substituted.
- Particularly suitable substituents are halogen, preferably chlorine, C 1 -C 10 -alkoxy, C 1 -C 20 -alkyl, aminoalkyl, C 1 -C 10 -mono- or -dialkylamino, acylamino, nitro, cyano, alkoxycarbonyl.
- Very particularly preferred compounds according to the invention are represented by the following formulas (IN) - (V).
- the compounds (III) and (IV) are particularly suitable for the photopolymerization with pure blue light of the wavelength of about 380-500 nm.
- X O, S, CHR 4 , NR 4 , preferably S, and n ranges from 1 to 4.
- R 4 is as defined above for the formulas (I) and (II). Examples of the invention in which X is NR 4 are as follows (formulas (VI) and (VII)):
- polymerization initiators according to formula (I) or (II) according to the invention which can be activated by the irradiation with visible light, are prepared according to the methods of Acta Cryst. (2005). E61, O1738-01741; Eur. J. Org. Chem. (1999). 1275-1290; or Synlett 2000, 371-373.
- polymerization initiators of the formula (I) or (II) according to the invention can be prepared by a novel process which comprises reacting the free N-hydroxy compound of the following formula
- R 3 is as defined above and is also part of the invention.
- X S, ie using N-Hydroxythiazolthionen as starting material described. The same applies to the other definitions of X above.
- the formation of the compound of the formula (I) or the formula (II) depends on the molar ratios of the starting materials used. At an approximately 1: 1 molar ratio of N-hydroxythiazolethione to carboxylic acid chloride, the compounds of formula (I) result in an approximately 2: 1 molar ratio of N-hydroxythiazolethione to bis (carboxylic acid chloride) resulting in the compounds of formula (II).
- the reaction takes place in an alkaline aqueous / organic medium (preferably an alkali metal carbonate in acetone) in a temperature range of 10 ° to 5O 0 C, preferably at ambient temperature (about 20 0 C).
- the starting materials are either commercially available or can be prepared by methods known to those skilled in the art.
- the polymerization initiators of the formula (I) or (II) according to the invention have a through hardening with a high degree of through-cure or a high penetration depth and can be used in a wide technical field. In addition, they have some significant advantages compared to already known UV and VIS photoinitiators. These include that the new initiators metal-free, easy to synthesize and can be used with, but in particular without amine co-initiators.
- the photoinitiators are weighed for the stated fields of application in amounts of 0.001 to 20 wt .-%, preferably 0.01 to 1 wt .-% and particularly preferably from 0.01 to 0.1 wt .-%, based on the monomer system.
- the photoinitiators can simply be stirred into the system used, which ensures a uniform distribution of the initiators and the transparency of the polymer.
- the photopolymerization can take place by means of solar radiation or by known methods of photopolymerization, that is to say by irradiation by means of light sources which emit the required wavelengths to a sufficient extent. Suitable wavelengths are 300 ⁇ ⁇ 780 nm, preferably 350 ⁇ ⁇ 600.
- the new compound can be used as a photoinitiator for photopolymerizable unsaturated compounds.
- unsaturated monomers such as esters of (meth) acrylic acid, e.g. Methyl, ethyl, n- or tert-butyl, isooctyl, hydroxyethyl, glycidyl or tetrahydrofufuryl (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl di (meth) acrylate, trimethylolpropane tri (meth) acrylate; Pentaerythritol tetra (meth) acrylate or pentaerythritol (meth) acrylate; Acrylonitrile, (meth) acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylamides; Vinyl esters such as e.g.
- Photopolymerizable compounds are also unsaturated oligomers or polymers and mixtures thereof with unsaturated monomers. These include thermoplastic resins containing unsaturated groups such as maleic acid esters, fumaric acid, allyl groups or acrylic or methacrylic groups. Examples of such oligomers are unsaturated polyesters, unsaturated acrylic resins and Polyetheracrylatoligomere. Examples of polyunsaturated compounds are especially the acrylates or methacrylates of diols and polyols, e.g. Hexamethylene di (meth) acrylate, trimethylene propane tri (meth) acrylate, or pentaerythritol tetra (meth) acrylate.
- polymerization may be carried out in the usual manner in emulsion, in reverse emulsion, in bulk or in solution.
- solvents water, aqueous organic solvents, purely organic solvents, solvent mixtures or ionic liquids can be used.
- the polymerization can also be carried out in supercritical carbon dioxide.
- the polymerization may in particular under for the radical polymerization typical conditions are carried out. The exact conditions are not critical and can be adjusted by the skilled person in the usual way.
- the invention further relates to the use of the above-described composition which comprises at least one free-radically polymerizable compound, in particular vinyl compound; and at least one compound of formula (I) and / or formula (II) as a radical initiator, as a coating material for technical, optical, medical applications and in photolithography.
- Photohardening is of particular importance for printing inks since the drying time of the binder decisively influences the production speed of the product.
- a photoinitiator according to the present invention which provides by visible light the polymerization-initializing species is suitable for use in photolithography.
- a substrate is coated with photopolymerizable monomers and irradiated certain areas of the substrate with visible light. Subsequently, the uncured fractions are rinsed out by means of solvents.
- three-dimensional structures can be constructed, as used for example in printing plates, or in a partial coating of silicon wafers.
- the light-curing compositions used for various purposes may contain fillers such as silica, gypsum, pigments, dyes, fibers, flow control agents or blowing agents, or other conventional additives, other than the photopolymerizable compounds and the corresponding photoinitiator.
- fillers such as silica, gypsum, pigments, dyes, fibers, flow control agents or blowing agents, or other conventional additives, other than the photopolymerizable compounds and the corresponding photoinitiator.
- X S (i.e., using an N-hydroxythiazole thione as a starting material), the synthesis proceeds as follows:
Abstract
The present invention relates to light curing compositions, comprising radically polymerizable vinyl compounds and daylight sensitive radical initiators of the formula (I) and/or (II), and optionally containing further additives, such as fillers, pigments, solvents, and to the use thereof as a coating material for technical, optical, and medical applications.
Description
Lichthärtende Zusammensetzungen Light-curing compositions
Die vorliegende Erfindung betrifft lichthärtende bzw. lichthärtbare Zusammensetzungen, die radikalisch polymerisierbare Verbindungen, insbesondere Vinylverbindungen und tageslichtsensitive Radikalinitiatoren umfassen und die gegebenenfalls weitere Additive wie Füllstoffe, Pigmente, Lösemittel enthalten, sowie deren Verwendung als Beschichtungsmaterial für technische, optische und medizinische Anwendungen. Außerdem betrifft die Erfindung aus den Zusammensetzungen hergestellte gehärtete Produkte einschließlich deren Herstellungsverfahren. Schließlich betrifft die Erfindung auch die als Radikalinitiatoren eingesetzten neuen Verbindungen als solche sowie ein Verfahren zu deren Herstellung.The present invention relates to light-curable or photocurable compositions comprising radically polymerizable compounds, in particular vinyl compounds and daylight-sensitive radical initiators and optionally further additives such as fillers, pigments, solvents, and their use as coating material for technical, optical and medical applications. Moreover, the invention relates to cured products prepared from the compositions, including their methods of preparation. Finally, the invention also relates to the novel compounds used as radical initiators as such and to a process for their preparation.
Photoinitiatoren absorbieren Strahlung im UV- oder im visuellen Bereich und stellen auf diese Weise die Polymerisation initialisierende Spezies zur Verfügung. Im Falle einer radikalischen Polymerisation sind dies freie Radikale. Allgemein werden radikalische Photoinitiatoren (Radikalinitiatoren), basierend auf dem chemischen Mechanismus der Radikalbildung in zwei Klassen eingeteilt. Norrish Typ I Photoinitiatoren bilden auf Grund von Strahlung durch unimolekularen Bindungsbruch freie Radikale. Dem Gegenüber durchlaufen Norrish Typ Il Photoinitiatoren, nach dem Aussetzen von Strahlung eine bimolekulare Reaktion, wobei der Photoinitiator mit einem zweiten Molekül (dem Coinitiator) reagiert und die Polymerisation initialisierende Spezies durch Elektronen- und Protonentransfer oder direkt durch Wasserstoffabstraktion bildet. Norrish Typ I und Il Photoinitiatoren werden bei die Härtung mit UV-Licht verwendet. Zurzeit werden fast ausschließlich Norrish Typ Il Photoinitiatoren für die Polymerisation durch Bestrahlung mit visuellem Licht verwendet.Photoinitiators absorb radiation in the UV or in the visual range, thus providing polymerization-initiating species. In the case of radical polymerization, these are free radicals. Generally, radical photoinitiators (radical initiators) are classified into two classes based on the chemical mechanism of radical formation. Norrish Type I photoinitiators form free radicals due to unimolecular bond breaking radiation. Opposite, Norrish Type II photoinitiators undergo a bimolecular reaction upon exposure to radiation, with the photoinitiator reacting with a second molecule (the coinitiator) and forming the polymerization initiating species by electron and proton transfer or directly by hydrogen abstraction. Norrish type I and II photoinitiators are used in curing with UV light. Currently, almost exclusively Norrish type II photoinitiators are used for polymerization by irradiation with visual light.
Charakteristisch für die Härtung durch Strahlung im UV-Bereich ist die hohe Reaktionsgeschwindigkeit. Diese Art der Härtung wird beispielsweise für Beschichtungen verschiedener Substrate wie zum Beispiel Holz verwendet. Ein solches Beispiel für UV-härtende Beschichtungen von Materialien mit Norrish Typ I Photoinitiatoren, wie Diethoxyphenylacetophenon oder Acrylphosphinoxiden, wird in
der EP 1247843 beschrieben. Ferner beschreibt die WO 01/51533 ein UV-härtendes Material zur Holzbeschichtung, wobei Acrylphosphinoxide, α-Hydroxyalkylphenone oder α-Dialkoxyacetophenone als Photoinitiatoren verwendet werden.Characteristic of the curing by radiation in the UV range is the high reaction rate. This type of curing is used for example for coatings of various substrates such as wood. Such an example of UV-curable coatings of materials with Norrish Type I photoinitiators, such as diethoxyphenylacetophenone or acrylic phosphine oxides, is disclosed in U.S. Pat EP 1247843. Further, WO 01/51533 describes a UV-curable wood-plating material using acrylphosphine oxides, α-hydroxyalkylphenones or α-dialkoxyacetophenones as photoinitiators.
Für alle transparenten Beschichtungen mit geringen Schichtdicken kann die UV- Härtung verwendet werden. Sie stößt jedoch bei einer Beimischung von Pigmenten und bei höheren Schichtdicken an ihre Grenzen. Solche photopolyreaktive Verbindungen härten deshalb durch UV-Strahlung nur unvollständig aus. Falls eine tiefere Durchhärtung gewünscht wird, wie zum Beispiel bei der Lichthärtung von Dentalmaterialien, die als Zahnfüllung verwendet werden sollen, kann zur Bestrahlung sichtbares Licht verwendet werden, welches eine höhere Durchdringstärke aufweist. Ein Photoinitiator der zu solchen Zwecken verwendet werden kann, ist eine Kombination aus α-Diketonen und Amino-Coinitiatoren. Ein solches System wird in der GB 1 ,408,265 beschrieben. Beispiele, in denen Dentalmaterialien und Photoinitiatoren verwendet werden, sind in der US 4,457,818, oder in der US 4,525,256, in denen Campherchinon bevorzugt verwendet wird, beschrieben. Campherchinon hat ein Absorptionsmaximum von 468 nm, was die intensive gelbe Farbe erklärt. Dies kann zum Nachteil haben, dass die Materialien, welche durch Campherchinon-Amin-Systeme als Photoinitiatoren gehärtet werden, einen unerwünschten sichtbaren gelben Schimmer aufweisen. Ein anderes System, das durch Strahlung im visuellen Bereich eine radikalische Polymerisation bzw. Härtung von Dentalmaterialien auslöst, beruht auf Acylgermanium-Verbindungen und wird in der US 2008/0076847 beschrieben.UV curing can be used for all transparent coatings with low layer thicknesses. However, it reaches its limits with an admixture of pigments and at higher layer thicknesses. Such photopoly-reactive compounds therefore cure only incompletely by UV radiation. If a deeper through cure is desired, such as in the photohardening of dental materials to be used as a dental filling, visible light may be used for irradiation which has a higher penetrating power. A photoinitiator that can be used for such purposes is a combination of α-diketones and amino coinitiators. Such a system is described in GB 1, 408,265. Examples in which dental materials and photoinitiators are used are described in US 4,457,818, or in US 4,525,256, in which camphor quinone is preferably used. Camphorquinone has an absorption maximum of 468 nm, which explains the intense yellow color. This may be to the disadvantage that the materials cured by camphorquinone-amine systems as photoinitiators have an undesirable visible yellow tinge. Another system which induces radical polymerization of dental materials by radiation in the visual field is based on acylgermanium compounds and is described in US 2008/0076847.
Es zeigt sich also, dass die im Stand der Technik bekannten Initiatorsysteme nicht in der Lage sind, in jedem Fall eine ausreichend schnelle und vollständige Aushärtung der gewünschten Materialien zu gewährleisten. Vielmehr haben die bekannten Verbindungen, die mittels kurzwelligem Licht (UV-Bereich) die Polymerisation initialisierende Spezies zur Verfügung stellen, den Nachteil, dass die kurzwellige Strahlung nur eine geringe Eindringtiefe erzielt. Das ist insbesondere bei Verwendung in Systemen mit Füllstoffen problematisch. Darüber hinaus waren keine Systeme verfügbar, die mittels sichtbarem Licht (Tageslicht) und ohne Coinitiatoren die Polymerisation initialisierende Spezies in einfacher Weise zur Verfügung stellen. Es bestand also weiterhin der dringende Bedarf an der Bereitsteilung neuer
einfacher, aber dennoch leistungsfähiger Initiatoren, die durch sichtbares Licht effizient aktiviert werden können.It thus turns out that the initiator systems known in the prior art are not capable of ensuring sufficiently rapid and complete curing of the desired materials in each case. Rather, the known compounds which provide by means of short-wave light (UV range) polymerization initializing species available, the disadvantage that the short-wave radiation achieves only a small penetration depth. This is particularly problematic when used in systems with fillers. Moreover, no systems were available that readily provide polymerization initiating species by means of visible light (daylight) and without coinitiators. Thus, there was still an urgent need to divide up new ones simple yet powerful initiators that can be efficiently activated by visible light.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, einen neuen Initiator für die radikalische Polymerisation zur Verfügung zu stellen, der bei Bestrahlung mit sichtbarem Licht (d.h. langwelligem Tageslicht) eine ausreichend schnelle und vollständige Aushärtung der gewünschten Materialien auch ohne Coinitiator und die genannten negativen Nebeneffekte gewährleistet.It is an object of the present invention to provide a novel radical polymerization initiator which, upon irradiation with visible light (ie, long wavelength daylight), provides sufficiently fast and complete cure of the desired materials, even without a coinitiator and negative side effects ,
Diese Aufgabe wurde überraschend durch die vorliegende Erfindung gemäß den angehängten Patentansprüchen gelöst.This object has surprisingly been achieved by the present invention according to the appended claims.
Die neuen Photoinitiatoren für die radikalische Polymerisation gemäß der Erfindung werden durch die Formeln (I) und (II) dargestellt, wobei es sich bei den Verbindungen der Formel (I) um die monomeren und bei denen der Formel (II) um die dimeren Strukturen handelt. Die dimeren Strukturen weisen eine annähernd gleiche Effizienz in der Initiatorwirkung auf, besitzen aber zudem noch eine geringere Diffusionsfähigkeit, was von praktischer Relevanz sein kann.The novel photoinitiators for radical polymerization according to the invention are represented by formulas (I) and (II) wherein the compounds of formula (I) are the monomers and those of formula (II) are the dimeric structures , The dimeric structures have approximately the same efficiency in the initiator effect, but also have a lower diffusibility, which may be of practical relevance.
Formeln (I) und (II):Formulas (I) and (II):
worin in den Formeln (I) und (II) jeweils unabhängig voneinanderwherein in the formulas (I) and (II) each independently
X = S, CHR4, O, oder NR4 darstellt;X = S, CHR 4 , O, or NR 4 ;
R1 und R2 jeweils unabhängig voneinander H, lineares oder verzweigtes C1-C20-R 1 and R 2 are each independently H, linear or branched C 1 -C 20
Alkyl; Thioalkyl; Aryl; oder Heteroaryl sind, wobei R1 und R2 auch miteinander verbunden sein können unter Bildung von gesättigten oder ungesättigten Cyclen oder Heterocyclen;
R3 = H, lineares oder verzweigtes C1-C20-Alkyl; Thioalkyl; Aryl; Heteroaryl ist; R4 = H, lineares oder verzweigtes C1-C20-Alkyl, wobei der Alkylsubstituent cyclische Teilstrukturen aufweisen kann; Acyloxy; Aryl; oder Heteroaryl ist; A eine aliphatische, aromatische oder heteroaromatische Verbindungsgruppe ist.alkyl; thioalkyl; aryl; or heteroaryl, wherein R 1 and R 2 may also be linked together to form saturated or unsaturated cyclics or heterocycles; R 3 = H, linear or branched C 1 -C 20 -alkyl; thioalkyl; aryl; Heteroaryl is; R 4 = H, linear or branched C 1 -C 20 -alkyl, where the alkyl substituent may have cyclic substructures; acyloxy; aryl; or heteroaryl; A is an aliphatic, aromatic or heteroaromatic compound group.
Die erfindungsgemäßen Polymerisationsinitiatoren nach Formel (I) oder (II) werden in lichthärtenden bzw. lichthärtbaren Zusammensetzung eingesetzt. Diese Zusammensetzungen umfassen: a. mindestens eine radikalisch polymerisierbare Verbindung, insbesondere Vinylverbindung; und b. mindestens eine Verbindung der Formel (I) und/oder der Formel (II) als Radikalinitiator.The polymerization initiators according to formula (I) or (II) according to the invention are used in light-curing or photocurable composition. These compositions comprise: a. at least one radically polymerizable compound, in particular vinyl compound; and b. at least one compound of formula (I) and / or formula (II) as a radical initiator.
Die Erfindung betrifft weiterhin das gehärtete Produkt, welches durch Lichthärtung dieser Zusammensetzung mit sichtbarem Licht erhältlich ist, sowie das Lichthärtungsverfahren zur Herstellung eines solchen gehärteten Produkts als solches.The invention further relates to the cured product obtainable by photohardening this composition with visible light, and to the photohardening process for producing such a cured product as such.
Außerdem betrifft die Erfindung insbesondere die Verwendung der Verbindungen der Formel (I) und/oder der Formel (II) als Radikalinitiator für die radikalische Polymerisation.In addition, the invention relates in particular to the use of the compounds of the formula (I) and / or of the formula (II) as radical initiator for free-radical polymerization.
Schließlich betrifft die Erfindung auch ein neues Herstellungsverfahren für die Verbindungen der Formel (I) und/oder der Formel (II).Finally, the invention also relates to a novel preparation process for the compounds of the formula (I) and / or of the formula (II).
Der Substituent R1 in den Formeln (I) und (II) kann vorzugsweise wie folgt variiert werden: R1 = H, C1-C20 Alkyl; Aryl, wobei Aryl ein ein- bis fünffach substituierter Phenyl-Substituent, ein ein- bis siebenfach substituierter Naphthalin-Substituent sein kann; Substituenten können Halogen, bevorzugt Chlor, Alkoxy, C1-C20-Alkyl, Aminoalkyl, Diaminoalkyl, Acylamino, Nitro, Cyano, Alkoxycarbonyl, wobei Alkoxy = C1-C10-Alkyl an einen einwertigen Sauerstoff-Substituenten gebunden ist; Acyloxy; Dialkylamino = ein oder zwei C1-C10 Alkyl an ein zweiwertiges Stickstoffatom gebunden; Acylamino = C1-C10-Alkanoyl oder substituiertes Benzoyl oder Naphthoyl an einen Aminostickstoff gebunden, sein.
Der Substituent R2 in den Formeln (I) und (II) kann vorzugsweise wie folgt variiert werden: R2 = H, C1-C20-Alkyl; Aryl, wobei Aryl ein ein- bis fünffach substituierter Phenyl-Substituent, ein ein- bis siebenfach substituierter Naphthalin-Substituent sein kann; Substituenten können Halogen, bevorzugt Chlor, Alkoxy, Dialkylamino, Acylamino, Methyl, Nitro, Cyano, Alkoxycarbonyl, wobei Alkoxy = C1-C10-Alkyl an einen einwertigen Sauerstoff-Substituenten gebunden; Acyloxy; Dialkylamino = ein oder zwei C1-C10-Alkyl an ein zweiwertiges Stickstoffatom gebunden, Acylamino = C1-C10-Alkanoyl oder substituiertes Benzoyl oder Naphthoyl an einen Aminostickstoff gebunden, sein; Heteroaryl, wobei vorzugsweise ein ein- bis vierfach substituierter Pyridin-Substituent, substituierte Thiazyl, Oxazyl und Imidazyl- Substituenten eingesetzt werden.The substituent R 1 in formulas (I) and (II) may preferably be varied as follows: R 1 = H, C 1 -C 20 alkyl; Aryl, wherein aryl may be a mono- to tri-substituted phenyl substituent, a monosubstituted to trisubstituted naphthalene substituent; Substituents may be halogen, preferably chloro, alkoxy, C 1 -C 20 alkyl, aminoalkyl, diaminoalkyl, acylamino, nitro, cyano, alkoxycarbonyl, wherein alkoxy = C 1 -C 10 alkyl is attached to a monovalent oxygen substituent; acyloxy; Dialkylamino = one or two C1-C10 alkyl bonded to a divalent nitrogen atom; Acylamino = C1-C10 alkanoyl or substituted benzoyl or naphthoyl bonded to an amino nitrogen. The substituent R 2 in the formulas (I) and (II) may preferably be varied as follows: R 2 = H, C 1 -C 20 -alkyl; Aryl, wherein aryl may be a mono- to tri-substituted phenyl substituent, a monosubstituted to trisubstituted naphthalene substituent; Substituents may be halogen, preferably chloro, alkoxy, dialkylamino, acylamino, methyl, nitro, cyano, alkoxycarbonyl, wherein alkoxy = C1-C10 alkyl is attached to a monovalent oxygen substituent; acyloxy; Dialkylamino = one or two C1-C10 alkyl bonded to a divalent nitrogen atom, acylamino = C1-C10 alkanoyl or substituted benzoyl or naphthoyl bonded to an amino nitrogen; Heteroaryl, wherein preferably a mono- to tetra-substituted pyridine substituent, substituted thiazole, oxazole and imidazyl substituents are used.
Der Substituent R3 in der Formel (I) kann vorzugsweise wie folgt variiert werden: R3 = H, C1-C20-Alkyl, vorzugsweise ein ein- bis fünffach substituierter Phenyl-Rest, ein ein- bis siebenfach substituierter Naphthalin-Substituent; Substituenten sind ausgewählt aus Halogen, bevorzugt Chlor, Methoxy, Methyl, Nitro, Cyano, Alkoxycarbonyl, wobei Alkoxy = C1-C10 Alkyl an einen einwertigen Sauerstoff- Substituengen gebunden; Acyloxy; Dialkylamino = ein oder zwei C1-C10 Alkyl an ein zweiwertiges Stickstoffatom gebunden, Acylamino = C1-C10 Alkanoyl oder substituiertes Benzoyl oder Naphthoyl an einen Aminostickstoff gebunden. Auch Ein- und Mehrfachkondensationsprodukte zwischen einer cyclischen Thiohydroxamsäure und einer substituierten Benzol-1 ,2-, -1 ,3- oder -1 ,4-dicarbonsäure oder einer Naphthalin-di-, tri-, -tetracarbonsäure können als R3 genannt werden. Weiterhin kann R3 ein heteroaromatischer Rest sein, wobei der Begriff heteroaroamtisch sich vorzugsweise auf Pyridin, Pyrrol, Thiophen und Furan sowie deren Derivate bezieht.The substituent R 3 in the formula (I) may preferably be varied as follows: R 3 = H, C 1 -C 20 -alkyl, preferably a mono- to quintuply-substituted phenyl radical, a monosubstituted to trisubstituted naphthalene substituent; Substituents are selected from halogen, preferably chloro, methoxy, methyl, nitro, cyano, alkoxycarbonyl, where alkoxy = C 1 -C 10 alkyl bonded to a monovalent oxygen substituent gene; acyloxy; Dialkylamino = one or two C1-C10 alkyl bonded to a divalent nitrogen atom, acylamino = C1-C10 alkanoyl or substituted benzoyl or naphthoyl bonded to an amino nitrogen. Also, single and multiple condensation products between a cyclic thiohydroxamic acid and a substituted benzene-1, 2-, -1, 3- or -1, 4-dicarboxylic acid or a naphthalene di-, tri-, tetracarboxylic can be mentioned as R 3 . Furthermore, R 3 may be a heteroaromatic radical, wherein the term heteroaroamtisch preferably refers to pyridine, pyrrole, thiophene and furan and derivatives thereof.
Der Substituent R4 in den Formeln (I) und (II) kann vorzugsweise wie folgt variiert werden: R4 = H, C1-C10-Alkyl, wobei ab C3 die Alkylkette linear oder verzweigt sein kann oder der Alkylsubstituent cyclische Teilstrukturen aufweisen kann, Phenyl, ein bis fünfach substituierte Phenylgruppen.The substituent R 4 in the formulas (I) and (II) can preferably be varied as follows: R 4 = H, C 1 -C 10 -alkyl, where from C 3 the alkyl chain can be linear or branched or the alkyl substituent can have cyclic substructures, Phenyl, one to five times substituted phenyl groups.
Die ringständige Gruppe X in den Formeln (I) und (II) kann bevorzugt wie folgt variiert werden, lautet aber besonders bevorzugt X = S. Formel (I) ist nachstehend beispielhaft angegeben.
CHR4, O, NR4 vorzugsweise SThe ring-shaped group X in the formulas (I) and (II) may preferably be varied as follows, but more preferably X = S. Formula (I) is exemplified below. CHR 4 , O, NR 4 preferably S
Bei den Verbindungen der Formel (II) ist A bevorzugt eine Pyridin-, Pyrrol-, Thiophen-, Furan-, Thiazol-, Oxazol- oder Imidazol-Gruppe oder ein Derivat davon oder eine ein- bis vierfach substituierte oder unsubstituierte Phenylengruppe.In the compounds of the formula (II), A is preferably a pyridine, pyrrole, thiophene, furan, thiazole, oxazole or imidazole group or a derivative thereof or a monosubstituted to tetra-substituted or unsubstituted phenylene group.
Bevorzugte Ausführungsformen der Erfindung weisen Verbindungen der Formel (I) bzw. (II) auf, worin X = S ist. Bevorzugt sind zudem R1, R2, R3 und R4 unabhängig voneinander H, C1-C20-Alkyl, Aryl, oder Heteroaryl; wobei Aryl einen ein- bis fünffach substituierten Phenyl-Substituenten oder einen ein- bis siebenfach substituierten Naphthalin-Substituenten bedeutet, wobei die Substituenten aus Halogen, insbesondere Chlor, C1-C10-Alkoxy, C1-C20-Alkyl, Aminoalkyl, C1-C10- Mono- oder -dialkylamino, Acylamino, Nitro, Cyano, Alkoxycarbonyl ausgewählt sind; und Heteroaryl substituiertes oder unsubstituiertes Pyridin, Pyrrol, Thiophen oder Furan bedeutet. Ferner ist A bevorzugt eine Pyridin-, Pyrrol-, Thiophen-, Furan-, Thiazol-, Oxazol- oder Imidazol-Gruppe oder ein Derivat davon oder eine ein- bis vierfach substituierte oder unsubstituierte Phenylengruppe ist. Die Definition der Substituenten an der Phenylengruppe entspricht der oben angeführten Definition. R2 ist in Formel (I) oder (II) besonders bevorzugt nicht H1 da bei diesen Verbindungen (d.h. in denen R2 C1-C20-Alkyl, Aryl, oder Heteroaryl wie oben definiert ist) eine überraschend höhere Sensitivität im sichtbaren Bereich des Lichts auftritt. Als Grund dafür wird eine bei Alkyl- und insbesondere Arylsubstituenten R2 bathochrome Verschiebung des längstwelligen Absorptionsmaximums des Chromophors (z.B. des Thiazol-2(3H)-chromophors) und eine damit verbundene höhere Sensivität im sichtbaren Bereich vermutet.Preferred embodiments of the invention have compounds of the formula (I) or (II) in which X = S. In addition, R 1 , R 2 , R 3 and R 4 are preferably independently of one another H, C 1 -C 20 -alkyl, aryl or heteroaryl; where aryl is a monosubstituted to trisubstituted phenyl substituent or a monosubstituted to trisubstituted naphthalene substituent, the substituents being selected from halogen, in particular chlorine, C 1 -C 10 -alkoxy, C 1 -C 20 -alkyl, aminoalkyl, C 1 -C 10 -alkyl, Mono- or dialkylamino, acylamino, nitro, cyano, alkoxycarbonyl; and heteroaryl is substituted or unsubstituted pyridine, pyrrole, thiophene or furan. Further, A is preferably a pyridine, pyrrole, thiophene, furan, thiazole, oxazole or imidazole group or a derivative thereof, or a mono- to tetra-substituted or unsubstituted phenylene group. The definition of the substituents on the phenylene group corresponds to the definition given above. R 2 in formula (I) or (II) is particularly preferably not H 1 because in these compounds (ie in which R 2 is C 1 -C 20 -alkyl, aryl or heteroaryl as defined above) a surprisingly higher sensitivity in the visible range of Light occurs. The reason for this is assumed to be a bathochromic shift of the longest-wavelength absorption maximum of the chromophore (eg of the thiazole-2 (3H) chromophore) in the case of alkyl and in particular aryl substituents R 2 and an associated higher sensitivity in the visible range.
Weiter bevorzugt sind Verbindungen der Formel (I), worin X=S ist, R1=C1-C4-Alkyl ist, R2= Phenyl oder ein Phenyl-Rest mit einem weiteren Ortho-, meta- oder paraständigen Substituenten ist, wobei der Substituent ausgewählt ist aus Methoxy, C1-
C4-Alkyl, Amino, Dialkylamino, Acylamino und Chlor; oder R1 und R2 einen ungesättigten Cyclus bilden; R3 = Phenyl oder ein Phenyl-Rest mit einem weiteren ortho-, meta oder para-ständigen Substituenten, ausgewählt aus Methoxy, C1-C4- Alkyl, Amino, Dialkylamino, Acylamino und Chlor, ist. Durch R1 und R2 gebildete ungesättigte Cyclen sind hier insbesondere Phenyl, Inden, Cumaron (Benzofuran), Indol, Thionaphthen (Benzothiophen), Naphthalin die substituiert sein können. Als Substituenten sind insbesondere Halogen, bevorzugt Chlor, C1-C10-Alkoxy, C1- C20-Alkyl, Aminoalkyl, C1-C10-Mono- oder -dialkylamino, Acylamino, Nitro, Cyano, Alkoxycarbonyl genannt.Further preferred are compounds of formula (I) wherein X is S, R 1 is C 1 -C 4 alkyl, R 2 is phenyl or a phenyl radical having another ortho, meta or para substituent, said Substituent is selected from methoxy, C1- C4 alkyl, amino, dialkylamino, acylamino and chloro; or R 1 and R 2 form an unsaturated cycle; R 3 = phenyl or a phenyl radical having another ortho, meta or para substituent selected from methoxy, C 1 -C 4 alkyl, amino, dialkylamino, acylamino and chloro. Unsaturated cyclics formed by R 1 and R 2 are especially phenyl, indene, coumarone (benzofuran), indole, thionaphthene (benzothiophene), naphthalene which may be substituted. Particularly suitable substituents are halogen, preferably chlorine, C 1 -C 10 -alkoxy, C 1 -C 20 -alkyl, aminoalkyl, C 1 -C 10 -mono- or -dialkylamino, acylamino, nitro, cyano, alkoxycarbonyl.
Ganz besonders bevorzugte Verbindungen gemäß der Erfindung sind durch die folgenden Formeln (IN)-(V) dargestellt. Dabei sind die Verbindungen (III) und (IV) besonders geeignet für die Photopolymerisation mit reinem Blaulicht der Wellenlänge von ungefähr 380-500 nm.Very particularly preferred compounds according to the invention are represented by the following formulas (IN) - (V). In this case, the compounds (III) and (IV) are particularly suitable for the photopolymerization with pure blue light of the wavelength of about 380-500 nm.
(III) (IV) (V)(III) (IV) (V)
In den Formeln (III) bis (V) bedeutet R5 = Chlor, Alkoxy, C1-C20-Alkyl, Aminoalkyl, Diaminoalkyl, Acylamino, Nitro, Cyano, Alkoxycarbonyl, wobei bedeutet: Alkoxy = C1-C10-Alkyl an einen einwertigen Sauerstoff-Substituenten gebunden; Acyloxy; Dialkylamino = ein oder zwei C1-C10-Alkyl an ein zweiwertiges Stickstoffatom gebunden; Acylamino = C1-C10-Alkanoyl oder substituiert Benzoyl oder Naphthoyl an einen Aminostickstoff gebunden. Ferner ist X = O, S, CHR4, NR4, bevorzugt S, und n reicht von 1 bis 4. R4 ist wie bei den Formeln (I) und (II) oben definiert.
Erfindungsgemäße Beispiele, in denen X = NR4 ist, lauten wie folgt (Formeln (VI) und (VII)):In the formulas (III) to (V), R 5 represents chlorine, alkoxy, C 1 -C 20 -alkyl, aminoalkyl, diaminoalkyl, acylamino, nitro, cyano, alkoxycarbonyl, wherein: alkoxy = C 1 -C 10 -alkyl to a monovalent oxygen -Substituenten bound; acyloxy; Dialkylamino = one or two C1-C10 alkyl bonded to a divalent nitrogen atom; Acylamino = C1-C10 alkanoyl or substituted benzoyl or naphthoyl bonded to an amino nitrogen. Further, X = O, S, CHR 4 , NR 4 , preferably S, and n ranges from 1 to 4. R 4 is as defined above for the formulas (I) and (II). Examples of the invention in which X is NR 4 are as follows (formulas (VI) and (VII)):
(VI) (VII)(VI) (VII)
Die erfindungsgemäßen Polymerisationsinitiatoren nach Formel (I) oder (II), welche durch die Bestrahlung mit sichtbarem Licht aktiviert werden können, sind gemäß den Verfahren aus Acta Cryst. (2005). E61 , O1738-01741 ; Eur. J. Org. Chem. (1999). 1275-1290; oder Synlett 2000, 371-373 zugänglich.The polymerization initiators according to formula (I) or (II) according to the invention, which can be activated by the irradiation with visible light, are prepared according to the methods of Acta Cryst. (2005). E61, O1738-01741; Eur. J. Org. Chem. (1999). 1275-1290; or Synlett 2000, 371-373.
Die erfindungsgemäßen Polymerisationsinitiatoren nach Formel (I) oder (II) können zudem nach einem neuen Verfahren hergestellt werden, welches die Umsetzung der freien N-Hydroxy-Verbindung der folgenden FormelIn addition, the polymerization initiators of the formula (I) or (II) according to the invention can be prepared by a novel process which comprises reacting the free N-hydroxy compound of the following formula
worin X, R1 und R2 wie oben definiert sind, mit einem Carbonsäurechlorid bzw. Bis(carbonsäurechlorid) einer der beiden folgenden Formelnwherein X, R 1 and R 2 are as defined above, with a carboxylic acid chloride or bis (carboxylic acid chloride) of one of the following two formulas
umfasst, worin R3 wie oben dfiniert ist, und ebenfalls Teil der Erfindung ist. Im folgenden wird die Synthese beispielhaft für die bevorzugte Ausführungsform mit X =
S, d.h. unter Einsatz von N-Hydroxythiazolthionen als Edukt, beschrieben. Analoges gilt aber auch für die anderen oben genannten Definitionen von X.wherein R 3 is as defined above and is also part of the invention. In the following the synthesis becomes exemplary for the preferred embodiment with X = S, ie using N-Hydroxythiazolthionen as starting material described. The same applies to the other definitions of X above.
Die Bildung der Verbindung der Formel (I) oder der Formel (II) hängt von den eingesetzten Molverhältnissen der Ausgangsprodukte ab. Bei einem annähernd 1 :1- Molverhältnis von N-Hydroxythiazolthion zu Carbonsäurechlorid resultieren die Verbindungen der Formel (I), bei einem annähernd 2:1 -Molverhältnis von N- Hydroxythiazolthion zu Bis(carbonsäurechlorid) resultieren die Verbindungen der Formel (II). Die Umsetzung erfolgt in einem alkalischen wässrig/organischem Medium (bevorzugt Alkalicarbonat in Aceton) in einem Temperaturbereich von 10° bis 5O0C, bevorzugt bei Umgebungstemperatur (ca. 200C). Die Ausgangsprodukte sind entweder kommerziell erhältlich oder können durch dem Fachmann bekannte Verfahren hergestellt werden.The formation of the compound of the formula (I) or the formula (II) depends on the molar ratios of the starting materials used. At an approximately 1: 1 molar ratio of N-hydroxythiazolethione to carboxylic acid chloride, the compounds of formula (I) result in an approximately 2: 1 molar ratio of N-hydroxythiazolethione to bis (carboxylic acid chloride) resulting in the compounds of formula (II). The reaction takes place in an alkaline aqueous / organic medium (preferably an alkali metal carbonate in acetone) in a temperature range of 10 ° to 5O 0 C, preferably at ambient temperature (about 20 0 C). The starting materials are either commercially available or can be prepared by methods known to those skilled in the art.
Vorteil gegenüber den bekannten Verfahren ist der Einsatz der freien N- Hydroxythiazolthione anstelle von deren Salzen, da die freien Säuren im Allgemeinen als Produkt der Thizaolthion-Synthese anfallen und im Gegensatz zu meist hygroskopischen Alkalimetallsalzen weder hygroskopisch sind noch basisch reagieren. Folglich zeichnet sich das neue Verfahren insbesondere durch eine höhere Effizienz und leichtere Handhabung der Edukte aus.Advantage over the known methods is the use of the free N-Hydroxythiazolthione instead of their salts, since the free acids generally incurred as a product of Thizaolthion synthesis and in contrast to most hygroscopic alkali metal salts are neither hygroscopic nor react basic. Consequently, the new process is characterized in particular by a higher efficiency and easier handling of the educts.
Die erfindungsgemäßen Polymerisationsinitiatoren nach Formel (I) oder (II) weisen eine Durchhärtung mit hohem Durchhärtungsgrad bzw. hoher Eindringtiefe auf und sind in einem breiten technischen Gebiet einsetzbar. Darüber hinaus weisen sie einige deutliche Vorteile im Vergleich zu schon bekannten UV- und VIS- Photoinitiatoren auf. Darunter fallen, dass die neuen Initiatoren metallfrei, einfach zu synthetisieren und mit, aber insbesondere auch ohne Amin-Coinitiatoren verwendet werden können. Die Photoinitiatoren werden für die angegebenen Anwendungsgebiete in Mengen von 0,001 bis 20 Gew.-%, vorzugsweise 0,01 bis 1 Gew.-% und besonders bevorzugt von 0,01 bis 0.1 Gew.-%, bezogen auf das Monomersystem eingewogen. Dabei können die Photoinitiatoren dank ihrer guten Löslichkeit einfach in das verwendete System eingerührt werden, was eine gleichmäßige Verteilung der Initiatoren und die Transparenz des Polymerisats gewährleistet.
Die Photopolymerisation kann mittels Sonneneinstrahlung, oder durch bekannte Methoden der Photopolymerisation, also durch Bestrahlung mittels Lichtquellen, welche die erforderlichen Wellenlängen im ausreichenden Maße emittieren, erfolgen. Geeignete Wellenlängen sind dabei 300 < λ < 780 nm, bevorzugt 350 < λ < 600.The polymerization initiators of the formula (I) or (II) according to the invention have a through hardening with a high degree of through-cure or a high penetration depth and can be used in a wide technical field. In addition, they have some significant advantages compared to already known UV and VIS photoinitiators. These include that the new initiators metal-free, easy to synthesize and can be used with, but in particular without amine co-initiators. The photoinitiators are weighed for the stated fields of application in amounts of 0.001 to 20 wt .-%, preferably 0.01 to 1 wt .-% and particularly preferably from 0.01 to 0.1 wt .-%, based on the monomer system. Thanks to their good solubility, the photoinitiators can simply be stirred into the system used, which ensures a uniform distribution of the initiators and the transparency of the polymer. The photopolymerization can take place by means of solar radiation or by known methods of photopolymerization, that is to say by irradiation by means of light sources which emit the required wavelengths to a sufficient extent. Suitable wavelengths are 300 <λ <780 nm, preferably 350 <λ <600.
Die neue Verbindung kann als Photoinitiator für photopolymerisierbare ungesättigte Verbindungen verwendet werden. Solche Verbindungen sind beispielsweise ungesättigte Monomere wie Ester von (Meth)acrylsäure, z.B. Methyl-, Ethyl-, n- oder tert-Butyl-, Isooctyl-, Hydroxyethyl-, Glycidyl- oder Tetrahydrofufuryl(meth)acrylat, Etylenglycoldi(meth)acrylat, Neopentyldi(meth)-acrylat, Trimethylolpropantri(meth)- acrylat; Pentaerythrittetra-(meth)acrylat oder Pentaerythritris(meth)acrylat; Acrylnitril, (Meth)acrylnitril, (Meth)acrylamid, N-substituierte (Meth)acrylamide; Vinylester wie z.B. Styrol, Alkylstyrole, Halogenstyrole, Divinylbenzol, Vinylnaphthalin, N- Vinylpyrrolidon, Vinylchlorid; Allylverbindungen wie Diallylphthalat, Diallylmaleat, Triallylisocyanurat, Triallylphosphat, oder Ethylenglycol-diallylether, und die Mischung von solchen ungesättigten Monomeren.The new compound can be used as a photoinitiator for photopolymerizable unsaturated compounds. Such compounds are, for example, unsaturated monomers such as esters of (meth) acrylic acid, e.g. Methyl, ethyl, n- or tert-butyl, isooctyl, hydroxyethyl, glycidyl or tetrahydrofufuryl (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl di (meth) acrylate, trimethylolpropane tri (meth) acrylate; Pentaerythritol tetra (meth) acrylate or pentaerythritol (meth) acrylate; Acrylonitrile, (meth) acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylamides; Vinyl esters such as e.g. Styrene, alkylstyrenes, halostyrenes, divinylbenzene, vinylnaphthalene, N-vinylpyrrolidone, vinyl chloride; Allyl compounds such as diallyl phthalate, diallyl maleate, triallyl isocyanurate, triallyl phosphate, or ethylene glycol diallyl ether, and the mixture of such unsaturated monomers.
Photopolymerisierbare Verbindungen sind weiterhin ungesättigte Oligomere oder Polymere und deren Mischungen mit ungesättigten Monomeren. Hierzu zählen thermoplastische Harze, die ungesättigte Gruppen wie Maleinsäureester, Fumarsäure, Allylgruppen oder Acryl- oder Methacrylgruppen enthalten. Beispiele für solche Oligomere sind ungesättigte Polyester, ungesättigte Acrylharze sowie Polyetheracrylatoligomere. Beispiele für mehrfach ungesättigte Verbindungen sind vor allem die Acrylate bzw. Methacrylate von Diolen und Polyolen z.B. Hexamethylendi(meth)acrylat, Trimethylenpropantri(meth)acrylat, oder Pentaerythrit- tetra(meth)acrylat.Photopolymerizable compounds are also unsaturated oligomers or polymers and mixtures thereof with unsaturated monomers. These include thermoplastic resins containing unsaturated groups such as maleic acid esters, fumaric acid, allyl groups or acrylic or methacrylic groups. Examples of such oligomers are unsaturated polyesters, unsaturated acrylic resins and Polyetheracrylatoligomere. Examples of polyunsaturated compounds are especially the acrylates or methacrylates of diols and polyols, e.g. Hexamethylene di (meth) acrylate, trimethylene propane tri (meth) acrylate, or pentaerythritol tetra (meth) acrylate.
Des Weiteren kann eine Polymerisation in gewohnter Weise in Emulsion, in umgekehrter Emulsion, in Substanz oder in Lösung durchgeführt werden. Als Lösemittel können Wasser, wässrige organische Lösemittel, rein organischen Lösemittel, Lösemittelgemische oder ionische Flüssigkeiten verwendet werden. Bei Verwendung einer transparenten Apparatur oder einer hochdruckstabilen Lichtquelle kann die Polymerisation auch in überkritischem Kohlendioxid durchgeführt werden. Die Polymerisation kann insbesondere unter für die radikalische Polymerisation
typischen Bedingungen durchgeführt werden. Die genauen Bedingungen sind unkritisch und können vom Fachmann in gewohnter Weise eingestellt werden.Furthermore, polymerization may be carried out in the usual manner in emulsion, in reverse emulsion, in bulk or in solution. As solvents, water, aqueous organic solvents, purely organic solvents, solvent mixtures or ionic liquids can be used. When using a transparent apparatus or a high-pressure-stable light source, the polymerization can also be carried out in supercritical carbon dioxide. The polymerization may in particular under for the radical polymerization typical conditions are carried out. The exact conditions are not critical and can be adjusted by the skilled person in the usual way.
Die Erfindung betrifft ferner die Verwendung der oben beschriebenen Zusammensetzung, welche mindestens eine radikalisch polymerisierbare Verbindung, insbesondere Vinylverbindung; und mindestens eine Verbindung der Formel (I) und/oder der Formel (II) als Radikalinitiator enthält, als Beschichtungsmaterial für technische, optische, medizinische Anwendungen sowie in der Photolithographie. Dabei hat die Photohärtung für Druckfarben besondere Bedeutung, da die Trocknungszeit des Bindemittels die Produktionsgeschwindigkeit des Produktes maßgeblich mitbestimmt. Ebenso ist die Photohärtung von Oberflächenbeschichtungen, wie sie bei der Lackierung von Blechen, oder Kunststoffteilen jeder Art anfällt, ein weiteres Einsatzgebiet. Auch hier besteht der Vorteil darin, dass durch die Bestrahlung mit sichtbarem Licht (Blaulicht) die Härtung initialisiert und somit auf die Bestrahlung mit für den Menschen schädlichen UV- Strahlen verzichtet werden kann. Ebenso ist ein Photoinitiator gemäß der vorliegenden Erfindung, welcher durch sichtbares Licht die zur Polymerisation initialisierende Spezies zur Verfügung stellt, für eine Verwendung in der Photolithographie geeignet. Hierbei wird ein Substrat mit photopolymerisierbaren Monomeren beschichtet und bestimmte Bereiche des Substrates mit sichtbarem Licht bestrahlt. Anschließend werden die ungehärteten Anteile mittels Lösemittel eruiert ausgespült. Auf diese Weise können mit Hilfe des neuen Photoinitiators dreidimensionale Strukturen aufgebaut werden, wie sie beispielsweise bei Druckplatten, oder bei einer Teilbeschichtung von Silicium-Wafern gebraucht werden. Die lichthärtenden Zusammensetzungen, wie sie für die verschiedensten Zwecke verwendet werden, können erfindungsgemäß außer den photopolymerisierbaren Verbindungen und dem entsprechenden Photoinitiator je nach Verwendungszweck Füllstoffe, wie Kieselsäure, Gips, Pigmente, Farbstoffe, Fasern, Verlaufsmittel oder Treibmittel, oder andere übliche Zusatzstoffe enthalten.The invention further relates to the use of the above-described composition which comprises at least one free-radically polymerizable compound, in particular vinyl compound; and at least one compound of formula (I) and / or formula (II) as a radical initiator, as a coating material for technical, optical, medical applications and in photolithography. Photohardening is of particular importance for printing inks since the drying time of the binder decisively influences the production speed of the product. Likewise, the photocuring of surface coatings, as obtained in the coating of sheets, or plastic parts of any kind, another field of application. Again, there is the advantage that by the irradiation with visible light (blue light) initializes the hardening and thus can be dispensed with the irradiation of harmful to humans UV rays. Also, a photoinitiator according to the present invention which provides by visible light the polymerization-initializing species is suitable for use in photolithography. Here, a substrate is coated with photopolymerizable monomers and irradiated certain areas of the substrate with visible light. Subsequently, the uncured fractions are rinsed out by means of solvents. In this way, with the help of the new photoinitiator three-dimensional structures can be constructed, as used for example in printing plates, or in a partial coating of silicon wafers. The light-curing compositions used for various purposes may contain fillers such as silica, gypsum, pigments, dyes, fibers, flow control agents or blowing agents, or other conventional additives, other than the photopolymerizable compounds and the corresponding photoinitiator.
Die Erfindung wird durch die folgenden Beispiele näher erläutert:
Anwendungsbeispiele:The invention is further illustrated by the following examples: Application examples:
1. Synthese der Verbindungen nach Formel (I) und (II):1. Synthesis of Compounds of Formula (I) and (II):
Die Herstellung der Verbindungen nach Formel (I) und (II) erfolgt erfindungsgemäß nach folgenden allgemeinen Schemata:The preparation of the compounds of formula (I) and (II) according to the invention according to the following general schemes:
Für die bevorzugte Ausführungsform X = S (d.h. unter Einsatz eines N- Hydroxythiazolthions als Edukt) verläuft die Synthese wie folgt:For the preferred embodiment, X = S (i.e., using an N-hydroxythiazole thione as a starting material), the synthesis proceeds as follows:
(I)
Eine Lösung aus N-Hydroxythiazolthion (1.00 mmol) in einem adäquaten Volumen Aceton wird mit K2CO3 (3 mmol) versetzt und 10 min bei 20 0C gerührt. Zu der Reaktionsmischung tropfenweise ein Carbonsäurechlorid (1.1 mmol) gegeben. Die Reaktionsmischung wird bei 20 0C nachgerührt. Die erhaltene Suspension wird mit Wasser versetzt, die Phasen getrennt und die wässrige Phase sukzessiv mit Diethylether und mit Ethylacetat extrahiert. Die organischen Phase wird mit den organischen Extrakten vereinigt und mit 2 M NaOH, sowie mit gesättigter wässriger NaCI-Lösung gewaschen. Die organische Phase wird abgetrennt, mit MgSO4 getrocknet und bei vermindertem Druck eingeengt. Der erhaltene Rückstand wird aus CH2CI2/Et2O/Pentan umkristallisiert.(I) A solution of N-hydroxythiazolethione (1.00 mmol) in an adequate volume of acetone is treated with K 2 CO 3 (3 mmol) and stirred at 20 0 C for 10 min. To the reaction mixture was added dropwise a carboxylic acid chloride (1.1 mmol). The reaction mixture is stirred at 20 0 C. Water is added to the resulting suspension, the phases are separated and the aqueous phase is extracted successively with diethyl ether and with ethyl acetate. The organic phase is combined with the organic extracts and washed with 2 M NaOH and with saturated aqueous NaCl solution. The organic phase is separated, dried with MgSO 4 and concentrated under reduced pressure. The residue obtained is recrystallized from CH 2 Cl 2 / Et 2 O / pentane.
2. Verwendung der Verbindungen nach Formel (I) und (II) als Photoinitiator:2. Use of the compounds of the formula (I) and (II) as photoinitiator:
Es werden in einem Schlenkkolben 2 g Monomer und 0,5 Gew.% Ethylenglycoldimethacrylat (EGDMA) als Vernetzer vorgelegt und so lange gerührt, bis eine homogene Lösung entstanden ist. Um die Polymerisation zu starten, wird zur Monomerlösung mit 0,07 Gew.% (1 ,4 mg/0, 0039 mmol) 5-(4-Methoxyphenyl)-4- methyl-2-thioxo-2,3-dihydro-1 ,3-thiazol-3-ylbenzoat eingerührt und das Polymerisat direkter Sonneneinstrahlung ausgesetzt. Bereits nach wenigen Minuten ist die Aushärtung soweit fortgeschritten, dass ein festes Polymer entstanden ist.2 g of monomer and 0.5% by weight of ethylene glycol dimethacrylate (EGDMA) are initially charged as cross-linking agent in a Schlenk flask and the mixture is stirred until a homogeneous solution has formed. To start the polymerization, to the monomer solution with 0.07 wt.% (1, 4 mg / 0, 0039 mmol) of 5- (4-methoxyphenyl) -4-methyl-2-thioxo-2,3-dihydro-1 , 3-thiazol-3-yl-benzoate stirred and the polymer exposed to direct sunlight. After just a few minutes curing has progressed so far that a solid polymer has been formed.
Die Ergebnisse sind der folgenden Tablelle 1 zu entnehmen.
The results are shown in the following Table 1.
Tab 1 AnwendungsbeispieleTab 1 Application examples
Monomer EGDMA Initiator AushärtungMonomer EGDMA initiator cure
(100 Gew. %) (Gew. %) (Gew. %) (Min.)(100 wt.%) (Wt.%) (Wt.%) (Min.)
Hydroxyethylmethacrylat 0,5 0,07Hydroxyethyl methacrylate 0.5 0.07
Vinylacetat 0,5 0,07 15 «Vinyl acetate 0.5 0.07 15 «
1 -Vinyl-2-pyroMdon 0,5 0,07 5-10 °1-vinyl-2-pyroMdon 0.5 0.07 5-10 °
Styrol 0,5 0,07 8-10 °Styrene 0.5 0.07 8-10 °
Methacrylsäure 0,5 0,07 5 *Methacrylic acid 0.5 0.07 5 *
Acrylnitril 0,5 0,07 20-30 n) Acrylonitrile 0.5 0.07 20-30 n)
Styrol+Maleinsäureanhydrid a) 0,5 0,07 30 n) Styrene + maleic anhydride a) 0.5 0.07 30 n)
a) Polymerisation in Lösung mit Toluol als LM ^ festes Polymer n) Polymerniederschlag a) Polymerization in solution with toluene as LM ^ solid polymer n ) polymer precipitate
*} Aushärtung nach Belichten mit Sonnenlicht bei direkter Sonneneinstrahlung im Monat Mai
*} Curing after exposure to sunlight in direct sunlight in the month of May
Claims
1. Lichthärtende Zusammensetzung, umfassend a. mindestens eine radikalisch polymerisierbare Verbindung; und b. mindestens eine Verbindung der Formel (I) und/oder der Formel (II) als Radikalinitiator,A light-curing composition comprising a. at least one radically polymerizable compound; and b. at least one compound of the formula (I) and / or of the formula (II) as free-radical initiator,
worin in den Formeln (I) und (II) jeweils unabhängig voneinanderwherein in the formulas (I) and (II) each independently
X = S, CHR4, O, oder NR4 darstellt;X = S, CHR 4 , O, or NR 4 ;
R1 und R2 jeweils unabhängig voneinander H, lineares oder verzweigtes C1-C20-R 1 and R 2 are each independently H, linear or branched C 1 -C 20
Alkyl; Thioalkyl; Aryl; oder Heteroaryl sind, wobei R1 und R2 auch miteinander verbunden sein können unter Bildung von gesättigten oder ungesättigten Cyclen oder Heterocyclen;alkyl; thioalkyl; aryl; or heteroaryl, wherein R 1 and R 2 may also be linked together to form saturated or unsaturated cyclics or heterocycles;
R3 = H, lineares oder verzweigtes C1-C20-Alkyl; Thioalkyl; Aryl; Heteroaryl ist;R 3 = H, linear or branched C 1 -C 20 -alkyl; thioalkyl; aryl; Heteroaryl is;
R4 = H, lineares oder verzweigtes C1-C20-Alkyl, wobei der Alkylsubstituent cyclische Teilstrukturen aufweisen kann; Acyloxy; Aryl; oder Heteroaryl ist;R 4 = H, linear or branched C 1 -C 20 -alkyl, where the alkyl substituent may have cyclic substructures; acyloxy; aryl; or heteroaryl;
A eine aliphatische, aromatische oder heteroaromatische Verbindungsgruppe ist.A is an aliphatic, aromatic or heteroaromatic compound group.
2. Zusammensetzung nach Anspruch 1 , worin2. A composition according to claim 1, wherein
X = S ist und/oderX = S is and / or
R1, R2, R3 und R4 unabhängig voneinander H, C1-C20-Alkyl, Aryl, oder Heteroaryl sind; wobei Aryl einen ein- bis fünffach substituierten Phenyl-Substituenten oder einen ein- bis siebenfach substituierten Naphthalin-Substituenten bedeutet, wobei dieR 1 , R 2 , R 3 and R 4 are independently H, C 1 -C 20 alkyl, aryl, or heteroaryl; where aryl is a monosubstituted to trisubstituted phenyl substituent or a monosubstituted to trisubstituted naphthalene substituent, where the
Substituenten aus Chlor, C1-C10-Alkoxy, C1-C20-Alkyl, Aminoalkyl, C1-C10-Mono- oder -dialkylamino, Acylamino, Nitro, Cyano, Alkoxycarbonyl ausgewählt sind; und Heteroaryl substituiertes oder unsubstituiertes Pyridin, Pyrrol, Thiophen oder Furan bedeutet; undSubstituents selected from chlorine, C 1 -C 10 alkoxy, C 1 -C 20 alkyl, aminoalkyl, C 1 -C 10 mono- or dialkylamino, acylamino, nitro, cyano, alkoxycarbonyl; and Heteroaryl is substituted or unsubstituted pyridine, pyrrole, thiophene or furan; and
A eine Pyridin-, Pyrrol-, Thiophen-, Furan-, Thiazol-, Oxazol- oder Imidazol-Gruppe oder ein Derivat davon oder eine substituierte oder unsubstituierte Phenylengruppe ist.A is a pyridine, pyrrole, thiophene, furan, thiazole, oxazole or imidazole group or a derivative thereof or a substituted or unsubstituted phenylene group.
3. Zusammensetzung nach Anspruch 1 und/oder 2, worin in der Formel (I) X=S ist, R1=C1-C4-Alkyl ist, R2= Phenyl oder ein Phenyl-Rest mit einem weiteren Ortho-, meta- oder para-ständigen Substituenten ist, wobei der Substituent ausgewählt ist aus Methoxy, C1-C4-Alkyl, Amino, Dialkylamino, Acyiamino und Chlor; oder R1 und R2 einen ungesättigten Cyclus bilden; R3 = Phenyl oder ein Phenyl-Rest mit einem weiteren Ortho-, meta oder para-ständigen Substituenten, ausgewählt aus Methoxy, C1-C4-Alkyl, Amino, Dialkylamino, Acyiamino und Chlor, ist.3. Composition according to claim 1 and / or 2, wherein in the formula (I) X is S, R 1 is C 1 -C 4 -alkyl, R 2 is phenyl or a phenyl radical with a further ortho, meta or para-substituent, wherein the substituent is selected from methoxy, C 1 -C 4 alkyl, amino, dialkylamino, acylamino and chloro; or R 1 and R 2 form an unsaturated cycle; R 3 = phenyl or a phenyl radical having another ortho, meta or para substituent selected from methoxy, C 1 -C 4 alkyl, amino, dialkylamino, acylamino and chloro.
4. Verwendung der Zusammensetzung nach einem der Ansprüche 1 bis 3 als Beschichtungsmaterial für technische, optische, medizinische Anwendungen sowie in der Photolithographie.4. Use of the composition according to any one of claims 1 to 3 as a coating material for technical, optical, medical applications and in photolithography.
5. Gehärtetes Produkt, welches durch Lichthärtung der Zusammensetzung nach einem der Ansprüche 1 bis 3 mit sichtbarem Licht erhältlich ist.5. A cured product obtainable by photocuring the composition of any of claims 1 to 3 with visible light.
6. Verfahren zur Herstellung eines gehärteten Produkts, welches das Härten der Zusammensetzung nach einem der Ansprüche 1 bis 3 durch Aussetzen gegenüber Tageslicht umfasst.6. A process for producing a cured product, which comprises curing the composition according to any one of claims 1 to 3 by exposure to daylight.
7. Verwendung des Produktes nach Anspruch 5 als Dentalmaterial, Druckfarbe, Lack, oder Oberflächenbeschichtung.7. Use of the product according to claim 5 as a dental material, printing ink, lacquer, or surface coating.
8. Verwendung der Verbindung der Formel (I) und/oder der Formel (II), wie sie in einem der Ansprüche 1 bis 3 definiert ist, als Radikalinitiator für die radikalische Polymerisation.8. Use of the compound of formula (I) and / or of formula (II) as defined in any one of claims 1 to 3, as radical initiator for the radical polymerization.
worinwherein
X = S, CHR4, O, oder NR4 darstellt;X = S, CHR 4 , O, or NR 4 ;
R1 und R2 jeweils unabhängig voneinander H, lineares oder verzweigtes C1-C20-R 1 and R 2 are each independently H, linear or branched C 1 -C 20
Alkyl; Thioalkyl; Aryl; oder Heteroaryl sind, wobei R1 und R2 auch miteinander verbunden sein können unter Bildung von gesättigten oder ungesättigten Cyclen oder Heterocyclen;alkyl; thioalkyl; aryl; or heteroaryl, wherein R 1 and R 2 may also be linked together to form saturated or unsaturated cyclics or heterocycles;
R3 = lineares oder verzweigtes C1-C20-Alkyl; Thioalkyl; Aryl; Heteroaryl ist;R 3 = linear or branched C 1 -C 20 -alkyl; thioalkyl; aryl; Heteroaryl is;
R4 = H, lineares oder verzweigtes C1-C20-Alkyl, wobei der Alkylsubstituent cyclische Teilstrukturen aufweisen kann; Acyloxy; Aryl; oder Heteroaryl ist;R 4 = H, linear or branched C 1 -C 20 -alkyl, where the alkyl substituent may have cyclic substructures; acyloxy; aryl; or heteroaryl;
mit der Maßgabe, dass (a) R2 nicht H ist, wenn X = S ist; und (b) nicht gleichzeitig X=S, R1 = Methyl, R2 = p-Methoxyphenyl und R3 = Phenyl sind.with the proviso that (a) R 2 is not H when X = S; and (b) not simultaneously X = S, R 1 = methyl, R 2 = p-methoxyphenyl and R 3 = phenyl.
10. Verbindung der Formel (II),10. compound of the formula (II)
worinwherein
X = S, CHR4, O, oder NR4 darstellt;X = S, CHR 4 , O, or NR 4 ;
R1 und R2 jeweils unabhängig voneinander H, lineares oder verzweigtes C1-C20-R 1 and R 2 are each independently H, linear or branched C 1 -C 20
Alkyl; Thioalkyl; Aryl; oder Heteroaryl sind, wobei R1 und R2 auch miteinander verbunden sein können unter Bildung von gesättigten oder ungesättigten Cyclen oder Heterocyclen; R4 = H, lineares oder verzweigtes C1-C20-Alkyl, wobei der Alkylsubstituent cyclische Teilstrukturen aufweisen kann; Acyloxy; Aryl; oder Heteroary! ist;alkyl; thioalkyl; aryl; or heteroaryl, wherein R 1 and R 2 may also be linked together to form saturated or unsaturated cyclics or heterocycles; R 4 = H, linear or branched C 1 -C 20 -alkyl, where the alkyl substituent may have cyclic substructures; acyloxy; aryl; or heteroary! is;
A eine aliphatische, aromatische oder heteroaromatische Verbindungsgruppe ist,A is an aliphatic, aromatic or heteroaromatic compound group,
mit der Maßgabe, dass R2 nicht H ist, wenn X = S ist.with the proviso that R 2 is not H when X = S.
11. Verfahren zur Herstellung der Verbindung nach Formel (I) oder (II)11. Process for the preparation of the compound of formula (I) or (II)
worin R1, R2, R3 und A wie in einem der Ansprüche 1 bis 3 definiert sind, welches die Umsetzung einer freien N-Hydroxy-Verbindung der folgenden Formelwherein R 1 , R 2 , R 3 and A are as defined in any one of claims 1 to 3, which is the reaction of a free N-hydroxy compound of the following formula
mit einem Carbonsäurechlorid oder einem Bis(carbonsäurechlorid) nach einer der beiden folgenden Formelnwith a carboxylic acid chloride or a bis (carboxylic acid chloride) according to one of the following two formulas
12. Verfahren nach Anspruch 11 , worin X = S ist. 12. The method of claim 11, wherein X = S.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101623624B1 (en) | 2013-06-19 | 2016-05-23 | 주식회사 엘지화학 | Photoactive compound, photosensitive resin composition comprising the photoactive compound, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material |
CN110105315A (en) * | 2019-04-30 | 2019-08-09 | 同济大学 | Oxime ester compound and its preparation method and application containing aryl thioethers furans or aryl thioethers thiophene |
CN112932708A (en) * | 2021-01-26 | 2021-06-11 | 杨洁 | Denture dyeing glazing patch and preparation method and application thereof |
CN114409830A (en) * | 2022-01-21 | 2022-04-29 | 深圳市普利凯新材料股份有限公司 | Naphthalimide photoinitiator, and synthesis method and application thereof |
CN114409830B (en) * | 2022-01-21 | 2023-07-28 | 深圳市普利凯新材料股份有限公司 | Naphthalimide photoinitiator, synthesis method and application thereof |
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