CA2059144C - Bisacylphosphine sulfides - Google Patents
Bisacylphosphine sulfides Download PDFInfo
- Publication number
- CA2059144C CA2059144C CA 2059144 CA2059144A CA2059144C CA 2059144 C CA2059144 C CA 2059144C CA 2059144 CA2059144 CA 2059144 CA 2059144 A CA2059144 A CA 2059144A CA 2059144 C CA2059144 C CA 2059144C
- Authority
- CA
- Canada
- Prior art keywords
- substituted
- unsubstituted
- halogen
- c12alkyl
- c4alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000003568 thioethers Chemical class 0.000 title abstract 2
- 229910052736 halogen Chemical group 0.000 claims abstract description 59
- 150000002367 halogens Chemical group 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 29
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 11
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims abstract description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 7
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims abstract 13
- 239000000203 mixture Substances 0.000 claims description 49
- 238000000576 coating method Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000007639 printing Methods 0.000 claims description 8
- 125000001511 cyclopentyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000008199 coating composition Substances 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 5
- -1 aromatic heterocyclic radical Chemical class 0.000 description 67
- 229920001577 copolymer Polymers 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 13
- 229920005862 polyol Polymers 0.000 description 12
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 150000004763 sulfides Chemical class 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 6
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000600 sorbitol Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005805 dimethoxy phenyl group Chemical group 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- YPZPOQVXHZOYPP-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphanyl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(CC(C)C)C(=O)C1=C(OC)C=CC=C1OC YPZPOQVXHZOYPP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940102838 methylmethacrylate Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 229920002601 oligoester Polymers 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NDXRPDJVAUCBOH-UHFFFAOYSA-N 2,6-dimethoxybenzoyl chloride Chemical compound COC1=CC=CC(OC)=C1C(Cl)=O NDXRPDJVAUCBOH-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- OSEDLTAGVNWCRO-UHFFFAOYSA-N 2-methyl-5-(2-methylprop-2-enoylamino)pent-2-enoic acid Chemical compound CC(=C)C(=O)NCCC=C(C)C(O)=O OSEDLTAGVNWCRO-UHFFFAOYSA-N 0.000 description 1
- UFFYQSOLZWNGSO-UHFFFAOYSA-N 2-methyl-n-[3-[1-[3-(2-methylprop-2-enoylamino)propoxy]ethoxy]propyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCCCOC(C)OCCCNC(=O)C(C)=C UFFYQSOLZWNGSO-UHFFFAOYSA-N 0.000 description 1
- TXBIZRLVIDXDGB-UHFFFAOYSA-N 2-methylpropylphosphane Chemical compound CC(C)CP TXBIZRLVIDXDGB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- UUHGHHYNVQDUEZ-UHFFFAOYSA-N 2-phenylisophosphindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)P1C1=CC=CC=C1 UUHGHHYNVQDUEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- XATDOBSAOBZFCA-UHFFFAOYSA-N 3-[4-(2-carboxyethenyl)cyclohexyl]prop-2-enoic acid Chemical compound OC(=O)C=CC1CCC(C=CC(O)=O)CC1 XATDOBSAOBZFCA-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- BEAWHIRRACSRDJ-UHFFFAOYSA-N OCC(CO)(CO)CO.OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O Chemical compound OCC(CO)(CO)CO.OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O BEAWHIRRACSRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- JYAOWJJDCMLXKZ-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphinothioyl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=S)(CC(C)C)C(=O)C1=C(OC)C=CC=C1OC JYAOWJJDCMLXKZ-UHFFFAOYSA-N 0.000 description 1
- GQPVFBDWIUVLHG-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)COC(=O)C(C)=C GQPVFBDWIUVLHG-UHFFFAOYSA-N 0.000 description 1
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- SWHLOXLFJPTYTL-UHFFFAOYSA-N [2-methyl-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(COC(=O)C(C)=C)COC(=O)C(C)=C SWHLOXLFJPTYTL-UHFFFAOYSA-N 0.000 description 1
- HSZUHSXXAOWGQY-UHFFFAOYSA-N [2-methyl-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)COC(=O)C=C HSZUHSXXAOWGQY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- GKRVGTLVYRYCFR-UHFFFAOYSA-N butane-1,4-diol;2-methylidenebutanedioic acid Chemical compound OCCCCO.OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GKRVGTLVYRYCFR-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 238000012505 colouration Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 125000004212 difluorophenyl group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- YQCFXPARMSSRRK-UHFFFAOYSA-N n-[6-(prop-2-enoylamino)hexyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCCNC(=O)C=C YQCFXPARMSSRRK-UHFFFAOYSA-N 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
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- GVEYKVGCJIJGIW-UHFFFAOYSA-N phenyl-bis(trimethylsilyl)phosphane Chemical compound C[Si](C)(C)P([Si](C)(C)C)C1=CC=CC=C1 GVEYKVGCJIJGIW-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001603 poly (alkyl acrylates) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- 150000003549 thiazolines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KKFOMYPMTJLQGA-UHFFFAOYSA-N tribenzyl phosphite Chemical compound C=1C=CC=CC=1COP(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 KKFOMYPMTJLQGA-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Bisacylphosphine sulfides of formula I
(See formula I) wherein R1 is unsubstituted C1-C18alkyl or C1-C8alkyl which is substituted by phenyl, -CN, C1-C12alkoxy or halogen, C1-C18alkenyl, unsubstituted C1-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl; C1-C12alkoxy or halogen, unsubsti-tuted C6-C12aryl or C6-C12aryl which is substituted by halogen, C1-C12alkyl or C1-C12alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted C1-C18alkyl or C1-C8alkyl which is substituted by phenyl,halogen or C1-C12alkoxy, C2-C6alkenyl, unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C12alkoxy or halogen, unsubstituted C6-C12ary1 or C6-C12aryl which is substituted by C1-C12alkyl, C1-C12alkoxy, C2-C12alkoxyalkyl, C1-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy are suitable initiators for the light-induced polymerisation of compounds containing ethylenically unsaturated double bonds.
(See formula I) wherein R1 is unsubstituted C1-C18alkyl or C1-C8alkyl which is substituted by phenyl, -CN, C1-C12alkoxy or halogen, C1-C18alkenyl, unsubstituted C1-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl; C1-C12alkoxy or halogen, unsubsti-tuted C6-C12aryl or C6-C12aryl which is substituted by halogen, C1-C12alkyl or C1-C12alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted C1-C18alkyl or C1-C8alkyl which is substituted by phenyl,halogen or C1-C12alkoxy, C2-C6alkenyl, unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C12alkoxy or halogen, unsubstituted C6-C12ary1 or C6-C12aryl which is substituted by C1-C12alkyl, C1-C12alkoxy, C2-C12alkoxyalkyl, C1-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy are suitable initiators for the light-induced polymerisation of compounds containing ethylenically unsaturated double bonds.
Description
~; a Bisacylphosphine sulfides The present invention relates to novel bisacylphosphine sulfides, to photocurable compositions which contain these compounds, to the use of bisacylphosphine sulfides as photoinitiators for the photopolymerisation of such compounds containing ethylenically unsaturated double bonds, and to a process for photopolymerising such compounds with bisacylphosphine sulfides as photoinitiators.
Monoacylphosphine sulfides and the use thereof as photoinitiators are disclosed in DE-A-3 034 697.
Bisacylphosphine oxides as initiators for light-induced polymerisation reactions are disclosed in EP-A-184 095.
K. Issleib et al. have reported in Z. anorg. allg. Chem. 408, 266-274, (1974) on the synthesis of cyclic carbonyl phosphides, as well as on the reaction of 2-phenyl-2-benzo-phospholene-1,3-dione with sulfur to the corresponding sulfide. The synthesis and spectroscopic data of the cited sulfide are also found in the paper by Andrew R. Baryon et al., published in J. Chem. Soc., Chem. Commun. (23), 1753-4, (1987).
It has now been found that bisacylphosphine sulfides are most effective photoinitiators for polymerising compounds containing ethylenically unsaturated double bonds.
Accordingly, the invention relates to compounds of formula I
O S O
II II II
R3-C ~ - C - R2 (~
R~
wherein R1 is unsubstituted C1-Clgalkyl or C1-C8alkyl which is substituted by phenyl, -CN, C1-Ct2alkoxy or halogen, C2-Clgalkenyl, unsubstituted CS-Cgcycloalkyl or CS-Cgcycloalkyl which is substituted by Ct-Ct2alkyl, Cl-Cl2alkoxy or halogen, unsubstituted C6-C12ary1 or C6-CtZaryl which is substituted by halogen, Cl-Ct2alkyl or C1-Cl2alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, Cl-C4alkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted Ct-Ct8alkyl or Cl-Cgalkyl which is substituted by phenyl, halogen or Cl-Cl2alkoxy, C2-C6alkenyl, unsubstituted CS-Cgcycloalkyl or CS-C8cycloalkyl which is substituted by Cl-Cl2alkyl, Cl-Cl2alkoxy or halogen, unsubstituted C6-C12ary1 or C6-C12ary1 which is substituted by Cl-Cl2alkyl, C1-Cl2alkoxy, C2-Cl2alkoxya.lkyl, Cl-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, Ct-C4alkyl or Cl-C4alkoxy.
R1, R2 and R3 as Cl-Cl8alkyl may be branched and unbranched alkyl, including methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, tert-hexyl, heptyl, 2,4,4-trimethylpentyl, octyl, nonyl, decyl, dodecyl, tetradecyl, heptadecyl or octadecyl. R1, R2 and R3 may preferably be Cl-Ct2alkyl.
R1, R2 and R3 as Ct-Cgalkyl which carries one or more, conveniently one to three and, preferably, one or two, substituents, may be benzyl, 1-phenylethyl, 2-phenylethyl, a,a-dimethylbenzyl, 2-methoxyethyl, 2-ethoxyethyl, diethoxymethyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl or trichloromethyl, and are preferably substituted Cl-C4alkyl, more particularly benzyl. R1 may also be cyanomethyl, cyanoethyl and the like.
R1 as C2-Clgalkenyl may be allyl, methallyl, 1,1-dimethylallyl, butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl or octadecenyl, and is preferably C2-Cl2alkenyl, most preferably C2-C6alkenyl.
R2 and R3 as C2-C6alkenyl may be vinyl, propenyl, butenyl or hexenyl.
R1, RZ and R3 as CS-Cgcycloalkyl may be cyclopentyl, cyclohexyl or cyclooctyl, preferably cyclopentyl and cyclohexyl, preferably cyclohexyl. R1, R2 and R3 as substituted CS-Cgcycloalkyl, conveniently mono- to tetrasubstituted CS-Cgcycloalkyl, may be methyl-cyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclo-hexyl, methoxycyclopentyl, dimethoxycyclopentyl, ethoxycyclopentyl, diethoxycyclo-pentyl, methoxycyclohexyl, dimethoxycyclohexyl, ethoxycyclohexyl, diethoxycyclohexyl, chlorocyclohexyl, chlorocyclopentyl, dichlorocyclohexyl or dichlorocyclopentyl. Substi-tuted cycloalkyl is preferably Ct-C4alkyl-substituted cycloalkyl.
Rt, R2 and R3 as C6-Cl2aryl may be phenyl, a-naphthyl, (3-naphthyl or 4-diphenylyl, preferably phenyl. R1, R2 and R3 as substituted C6-C12ary1 preferably carry 1 to 3 substituents and may be chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, tolyl, mesityl, ethylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxy-phenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaph-thyl or ethoxynaphthyl, preferably dimethoxyphenyl, chlorophenyl and mesityl, preferably dimethoxyphenyl. R2 and R3 as substituted aryl may also be methoxyethylphenyl, ethoxy-methylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
Alkyl and alkoxy as substituents of aryl contain 1 to 4 carbon atoms and are preferably methyl or methoxy.
A heterocyclic radical Rt, R2 and R3 may be mononuclear or polynuclear, preferably mono- or binuclear, typically with a fused benzene ring, and may be furyl, thienyl, pyrrolyl, pyridyl, indolyl, benzoxazolyl, benzimidazolyl or benzothiazolyl.
Such a hetero-cyclic radical preferably contains 4 to 12 carbon atoms. These heterocyclic radicals may carry one or more, conveniently one or two, substituents. Illustrative examples are dimethylpyridyl, methylquinolyl, dimethylpyrrolyl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
Halogen is preferably chloro, bromo or fluoro, most preferably chloro.
A preferred embodiment of the invention relates to compounds of formula I, wherein Rt is unsubstituted C1-Cl2alkyl or Cl-C8alkyl which is substituted by phenyl, -CN, Ct-C4alkoxy or halogen, CZ-Ct2alkenyl, unsubstituted CS-Cgcycloalkyl or CS-C8cyclo-alkyl which is substituted by Ct-Ct2alkyl, Cl-C4alkoxy or halogen, unsubstituted C6-Cl2aryl or C6-Cl2aryl which is substituted by halogen, Ct-Cl2alkyl or Cl-C4alkoxy or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or Ct-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted Ct-Cl2alkyl or Ct-Cgalkyl which is substituted by phenyl, halogen or Ct-C4alkoxy, C2-C6alkenyl, unsubstituted CS-Cgcycloalkyl or CS-C8cycloalkyl which is substituted by Ct-Ct2alkyl, Ct-C4alkoxy or halogen, unsubstituted C6-C12ary1 or C6-Ct2ary1 which is substituted by C1-Cl2alkyl, C1-C4alkoxy, C2-Cgalkoxyalkyl, Ct-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy.
Interesting compounds are also those of formula I, wherein Rt is unsubstituted C1-Cl2alkyl or C1-C4alkyl which is substituted by phenyl, -CN, C1-C4alkoxy or halogen, C2-C6alkenyl, or unsubstituted CS-Cgcycloalkyl or CS-Cgcycloalkyl which is substituted by Cl-Cl2alkyl, C1-C4alkoxy or halogen, or unsubstituted C6C12ary1 or C6C12ary1 which is substituted by halogen, C1-Cl2alkyl or C1-C4allcoxy and R2 and R3 are each independently of the other unsubstituted C1-Cl2alkyl or Cl-C4alkyl which is substituted by phenyl, halogen or Cl-C4alkoxy, C2-C6alkenyl, or unsubstituted CS-Cgcycloalkyl or CS-C8cyclo-alkyl which is substituted by C1-Cl2alkyl, Cl-C4alkoxy or halogen, or unsubstituted C6-Cl2aryl or C6-Ci2aryl which is substituted by Cl-Cl2alkyl, Cl-C4alkoxy, C2-CBalkoxy-alkyl, C1-C4alkylthio or halogen.
Other preferred compounds of formula I are those wherein Rl is unsubstituted C1-Cl2alkyl, phenyl-Cl-C4alkyl, unsubstituted or Ci-Cl2alkyl-substituted cyclopentyl or cyclohexyl, or unsubstituted phenyl or phenyl which is substituted by halogen, C1-ClZalkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted Cl-Cl2alkyl, phenyl-Cl-C4alkyl, unsubstituted or Ct-Ct2alkyl-substituted cyclopentyl or cyclohexyl, or unsubstituted phenyl or phenyl which is substituted by C1-Cl2alkyl, C1-C4alkoxy or halogen.
Also preferred are those compounds of formula I wherein R1 is Ci-Cl2alkyl, cyclohexyl or phenyl-Cl-C4alkyl, and R2 and R3 are each independently of the other phenyl which is substituted by Cl-C4alkoxy, halogen or Cl-C4alkyl.
Interesting compounds of formula I are also those wherein R2 and R3 are identical.
Compounds of formula I which also merit interest are those wherein Rt is Cl-C8alkyl or benzyl and R2 and R3 are Cl-C4alkyl- or C1-C4alkoxy-substituted phenyl.
The compounds of formula I may be prepared by reacting the appropriate phosphines with elemental sulfur:
O O O S O
R3-C-P-CI-R2 + S ~ R3-C-IP-C-R2 I I
R~ R~
Monoacylphosphine sulfides and the use thereof as photoinitiators are disclosed in DE-A-3 034 697.
Bisacylphosphine oxides as initiators for light-induced polymerisation reactions are disclosed in EP-A-184 095.
K. Issleib et al. have reported in Z. anorg. allg. Chem. 408, 266-274, (1974) on the synthesis of cyclic carbonyl phosphides, as well as on the reaction of 2-phenyl-2-benzo-phospholene-1,3-dione with sulfur to the corresponding sulfide. The synthesis and spectroscopic data of the cited sulfide are also found in the paper by Andrew R. Baryon et al., published in J. Chem. Soc., Chem. Commun. (23), 1753-4, (1987).
It has now been found that bisacylphosphine sulfides are most effective photoinitiators for polymerising compounds containing ethylenically unsaturated double bonds.
Accordingly, the invention relates to compounds of formula I
O S O
II II II
R3-C ~ - C - R2 (~
R~
wherein R1 is unsubstituted C1-Clgalkyl or C1-C8alkyl which is substituted by phenyl, -CN, C1-Ct2alkoxy or halogen, C2-Clgalkenyl, unsubstituted CS-Cgcycloalkyl or CS-Cgcycloalkyl which is substituted by Ct-Ct2alkyl, Cl-Cl2alkoxy or halogen, unsubstituted C6-C12ary1 or C6-CtZaryl which is substituted by halogen, Cl-Ct2alkyl or C1-Cl2alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, Cl-C4alkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted Ct-Ct8alkyl or Cl-Cgalkyl which is substituted by phenyl, halogen or Cl-Cl2alkoxy, C2-C6alkenyl, unsubstituted CS-Cgcycloalkyl or CS-C8cycloalkyl which is substituted by Cl-Cl2alkyl, Cl-Cl2alkoxy or halogen, unsubstituted C6-C12ary1 or C6-C12ary1 which is substituted by Cl-Cl2alkyl, C1-Cl2alkoxy, C2-Cl2alkoxya.lkyl, Cl-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, Ct-C4alkyl or Cl-C4alkoxy.
R1, R2 and R3 as Cl-Cl8alkyl may be branched and unbranched alkyl, including methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, tert-hexyl, heptyl, 2,4,4-trimethylpentyl, octyl, nonyl, decyl, dodecyl, tetradecyl, heptadecyl or octadecyl. R1, R2 and R3 may preferably be Cl-Ct2alkyl.
R1, R2 and R3 as Ct-Cgalkyl which carries one or more, conveniently one to three and, preferably, one or two, substituents, may be benzyl, 1-phenylethyl, 2-phenylethyl, a,a-dimethylbenzyl, 2-methoxyethyl, 2-ethoxyethyl, diethoxymethyl, 2-butoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl or trichloromethyl, and are preferably substituted Cl-C4alkyl, more particularly benzyl. R1 may also be cyanomethyl, cyanoethyl and the like.
R1 as C2-Clgalkenyl may be allyl, methallyl, 1,1-dimethylallyl, butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl or octadecenyl, and is preferably C2-Cl2alkenyl, most preferably C2-C6alkenyl.
R2 and R3 as C2-C6alkenyl may be vinyl, propenyl, butenyl or hexenyl.
R1, RZ and R3 as CS-Cgcycloalkyl may be cyclopentyl, cyclohexyl or cyclooctyl, preferably cyclopentyl and cyclohexyl, preferably cyclohexyl. R1, R2 and R3 as substituted CS-Cgcycloalkyl, conveniently mono- to tetrasubstituted CS-Cgcycloalkyl, may be methyl-cyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclo-hexyl, methoxycyclopentyl, dimethoxycyclopentyl, ethoxycyclopentyl, diethoxycyclo-pentyl, methoxycyclohexyl, dimethoxycyclohexyl, ethoxycyclohexyl, diethoxycyclohexyl, chlorocyclohexyl, chlorocyclopentyl, dichlorocyclohexyl or dichlorocyclopentyl. Substi-tuted cycloalkyl is preferably Ct-C4alkyl-substituted cycloalkyl.
Rt, R2 and R3 as C6-Cl2aryl may be phenyl, a-naphthyl, (3-naphthyl or 4-diphenylyl, preferably phenyl. R1, R2 and R3 as substituted C6-C12ary1 preferably carry 1 to 3 substituents and may be chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, tolyl, mesityl, ethylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxy-phenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaph-thyl or ethoxynaphthyl, preferably dimethoxyphenyl, chlorophenyl and mesityl, preferably dimethoxyphenyl. R2 and R3 as substituted aryl may also be methoxyethylphenyl, ethoxy-methylphenyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
Alkyl and alkoxy as substituents of aryl contain 1 to 4 carbon atoms and are preferably methyl or methoxy.
A heterocyclic radical Rt, R2 and R3 may be mononuclear or polynuclear, preferably mono- or binuclear, typically with a fused benzene ring, and may be furyl, thienyl, pyrrolyl, pyridyl, indolyl, benzoxazolyl, benzimidazolyl or benzothiazolyl.
Such a hetero-cyclic radical preferably contains 4 to 12 carbon atoms. These heterocyclic radicals may carry one or more, conveniently one or two, substituents. Illustrative examples are dimethylpyridyl, methylquinolyl, dimethylpyrrolyl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
Halogen is preferably chloro, bromo or fluoro, most preferably chloro.
A preferred embodiment of the invention relates to compounds of formula I, wherein Rt is unsubstituted C1-Cl2alkyl or Cl-C8alkyl which is substituted by phenyl, -CN, Ct-C4alkoxy or halogen, CZ-Ct2alkenyl, unsubstituted CS-Cgcycloalkyl or CS-C8cyclo-alkyl which is substituted by Ct-Ct2alkyl, Cl-C4alkoxy or halogen, unsubstituted C6-Cl2aryl or C6-Cl2aryl which is substituted by halogen, Ct-Cl2alkyl or Cl-C4alkoxy or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or Ct-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted Ct-Cl2alkyl or Ct-Cgalkyl which is substituted by phenyl, halogen or Ct-C4alkoxy, C2-C6alkenyl, unsubstituted CS-Cgcycloalkyl or CS-C8cycloalkyl which is substituted by Ct-Ct2alkyl, Ct-C4alkoxy or halogen, unsubstituted C6-C12ary1 or C6-Ct2ary1 which is substituted by C1-Cl2alkyl, C1-C4alkoxy, C2-Cgalkoxyalkyl, Ct-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy.
Interesting compounds are also those of formula I, wherein Rt is unsubstituted C1-Cl2alkyl or C1-C4alkyl which is substituted by phenyl, -CN, C1-C4alkoxy or halogen, C2-C6alkenyl, or unsubstituted CS-Cgcycloalkyl or CS-Cgcycloalkyl which is substituted by Cl-Cl2alkyl, C1-C4alkoxy or halogen, or unsubstituted C6C12ary1 or C6C12ary1 which is substituted by halogen, C1-Cl2alkyl or C1-C4allcoxy and R2 and R3 are each independently of the other unsubstituted C1-Cl2alkyl or Cl-C4alkyl which is substituted by phenyl, halogen or Cl-C4alkoxy, C2-C6alkenyl, or unsubstituted CS-Cgcycloalkyl or CS-C8cyclo-alkyl which is substituted by C1-Cl2alkyl, Cl-C4alkoxy or halogen, or unsubstituted C6-Cl2aryl or C6-Ci2aryl which is substituted by Cl-Cl2alkyl, Cl-C4alkoxy, C2-CBalkoxy-alkyl, C1-C4alkylthio or halogen.
Other preferred compounds of formula I are those wherein Rl is unsubstituted C1-Cl2alkyl, phenyl-Cl-C4alkyl, unsubstituted or Ci-Cl2alkyl-substituted cyclopentyl or cyclohexyl, or unsubstituted phenyl or phenyl which is substituted by halogen, C1-ClZalkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted Cl-Cl2alkyl, phenyl-Cl-C4alkyl, unsubstituted or Ct-Ct2alkyl-substituted cyclopentyl or cyclohexyl, or unsubstituted phenyl or phenyl which is substituted by C1-Cl2alkyl, C1-C4alkoxy or halogen.
Also preferred are those compounds of formula I wherein R1 is Ci-Cl2alkyl, cyclohexyl or phenyl-Cl-C4alkyl, and R2 and R3 are each independently of the other phenyl which is substituted by Cl-C4alkoxy, halogen or Cl-C4alkyl.
Interesting compounds of formula I are also those wherein R2 and R3 are identical.
Compounds of formula I which also merit interest are those wherein Rt is Cl-C8alkyl or benzyl and R2 and R3 are Cl-C4alkyl- or C1-C4alkoxy-substituted phenyl.
The compounds of formula I may be prepared by reacting the appropriate phosphines with elemental sulfur:
O O O S O
R3-C-P-CI-R2 + S ~ R3-C-IP-C-R2 I I
R~ R~
This method is described in DE-A-3 034 697 for the preparation of monoacylphosphine sulfides. The bisacylphosphines are reacted as such or in a suitable inert organic solvent, as in a hydrocarbon such as toluene, cyclohexane or chlorobenzene, or in an aliphatic or aromatic ether, such as dibutyl ether, dioxane, diethylene glycol dimethyl ether or diphenyl ether, with an equimolar amount of elemental sulfur. The resultant bisacylphosphine sulfide, or solution thereof, is freed by filtration from any remaining sulfur. The reaction is conveniently carried out in an inert gas atmosphere, as in nitrogen, argon or carbon dioxide, preferably nitrogen. The reaction temperatures are in the range from 20 to 200°C, preferably from 60 to 120°C, depending on the solvent and the educts.
After removal of the solvent, the bisacylphosphine sulfide can be isolated in pure form by distillation or recrystallisation.
The preparation of the bisacylphosphine starting materials is known from the literature to those skilled in the art and is described, for example, in EP-A-184 095. Thus they may be prepared by reacting a suitable acid halide with a phosphine in the presence of a base, preferably an amine base. The phosphine used in this reaction may conveniently be bis(trimethylsilyl)phenylphosphine. In the reaction with the acid halide, the trimethylsilyl groups are then replaced by the acid radical.
The invention further relates to compositions comprising (a) at least one ethylenically unsaturated photopolymerisable compound and (b) at least one compound of formula I.
In the practice of this invention, the compounds of formula I can be used as photoinitiators for the photopolymerisation of ethylenically unsaturated compounds or mixtures which contain such compounds. Component (a) may suitably be selected from ethylenically unsaturated monomers, oligomers and polymers which react by photopolymerisation to form products of high molecular weight and thereby change their solubility.
The unsaturated compounds may contain one or more olefinic double compounds.
They may be low molecular weight compounds (monomers) or high molecular weight compounds (oligomers).
Particularly suitable unsaturated compounds include esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, including unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene, .~
After removal of the solvent, the bisacylphosphine sulfide can be isolated in pure form by distillation or recrystallisation.
The preparation of the bisacylphosphine starting materials is known from the literature to those skilled in the art and is described, for example, in EP-A-184 095. Thus they may be prepared by reacting a suitable acid halide with a phosphine in the presence of a base, preferably an amine base. The phosphine used in this reaction may conveniently be bis(trimethylsilyl)phenylphosphine. In the reaction with the acid halide, the trimethylsilyl groups are then replaced by the acid radical.
The invention further relates to compositions comprising (a) at least one ethylenically unsaturated photopolymerisable compound and (b) at least one compound of formula I.
In the practice of this invention, the compounds of formula I can be used as photoinitiators for the photopolymerisation of ethylenically unsaturated compounds or mixtures which contain such compounds. Component (a) may suitably be selected from ethylenically unsaturated monomers, oligomers and polymers which react by photopolymerisation to form products of high molecular weight and thereby change their solubility.
The unsaturated compounds may contain one or more olefinic double compounds.
They may be low molecular weight compounds (monomers) or high molecular weight compounds (oligomers).
Particularly suitable unsaturated compounds include esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, including unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene, .~
polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene, copolymers, polyisoprene and isoprene copolymers, polymers and coplymers containing (meth)acrylic groups in side-chains, as well as mixtures of one or more such polymers.
Unsaturated carboxylic acids are typically acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids, such as linolenic acid or oleic acid.
Acrylic acid and methacrylic acid are preferred.
Suitable polyols are aromatic polyols and, preferably, aliphatic and cycloaliphatic polyols.
Illustrative examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, as well as novolaks and resols. Polyepoxides include those based on the cited polyols, preferably on the aromatic polyols and epichlorohydrin.
Further suitable polyols are polymers and copolymers, which contain hydroxyl groups in the polymer chain or in side groups, for example polyvinyl alcohol and copolymers thereof or polymethacrylic hydroxyalkyl esters or copolymers thereof. Other suitable polyols are oligoesters containing hydroxyl end groups.
Illustrative examples of aliphatic and cycloaliphatic polyols are alkylenediols containing preferably 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxy-methylcyclohexane, glycerol, tris((3-hydroxyethyl)amine, trimethylolethane, trimethylol-propane, pentaerythritol, dipentaerythritol and sorbitol.
The polyols may be esterified partially or completely with one or with different unsaturated carboxylic acids, in which case the free hydroxyl groups of the partial esters may be modified, for example etherified, or esterified with other carboxylic acids.
Illustrative examples of esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentacrylate, dipentaerythritol hexacrylate, tripenta-erythritol octacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, kG.
-..~
Unsaturated carboxylic acids are typically acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids, such as linolenic acid or oleic acid.
Acrylic acid and methacrylic acid are preferred.
Suitable polyols are aromatic polyols and, preferably, aliphatic and cycloaliphatic polyols.
Illustrative examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, as well as novolaks and resols. Polyepoxides include those based on the cited polyols, preferably on the aromatic polyols and epichlorohydrin.
Further suitable polyols are polymers and copolymers, which contain hydroxyl groups in the polymer chain or in side groups, for example polyvinyl alcohol and copolymers thereof or polymethacrylic hydroxyalkyl esters or copolymers thereof. Other suitable polyols are oligoesters containing hydroxyl end groups.
Illustrative examples of aliphatic and cycloaliphatic polyols are alkylenediols containing preferably 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxy-methylcyclohexane, glycerol, tris((3-hydroxyethyl)amine, trimethylolethane, trimethylol-propane, pentaerythritol, dipentaerythritol and sorbitol.
The polyols may be esterified partially or completely with one or with different unsaturated carboxylic acids, in which case the free hydroxyl groups of the partial esters may be modified, for example etherified, or esterified with other carboxylic acids.
Illustrative examples of esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentacrylate, dipentaerythritol hexacrylate, tripenta-erythritol octacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, kG.
-..~
dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipenta-erythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol-modified triacrylate, sorbitol tetramethacrylate, sorbitol pentacrylate, sorbitol hexacrylate, oligoester acrylates and methacrylates, glycerol di- and -triacrylate, 1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycol having molecular weights of 200 to 1500, or mixtures thereof.
Also suitable for use as component (a) are the amides of identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines containing preferably 2 to 6, more particularly 2 to 4, amino groups. Exemplary of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-di-aminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, bis(~3-aminoethyl) ether, diethylenetriamine, triethylenetetramine, bis((3-aminoethoxy)ethane or bis((3-aminopropoxy)ethane. Other suitable polyamines are polymers and copolymers which may contain additional amino groups in the side-chain and oligoamides containing amino end groups.
Exemplary of such unsaturated amides are: methylenebisacrylamide, 1,6-hexamethylene-bisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)-ethane, (3-methacrylamidoethylmethacrylate, N-[((3-hydroxyethoxy)ethyl]acrylamide.
Suitable unsaturated polyesters and polyamides are derived typically from malefic acid and diols or diamines. Malefic acid can be partially replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, as with styrene. The polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from those with long chains containing typically from 6 to 20 carbon atoms. Polyurethanes are typically those derived from saturated or unsaturated diisocyanates and unsaturated and saturated diols.
Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers include olefins such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene or vinyl chloride. Polymers containing (meth)acrylate groups in the side-chain are _g_ also known. They may typically be reaction products of epoxy resins based on novolak with (meth)acrylic acid, homo- or copolymers of polyvinyl alcohol or their hydroxyalkyl derivatives which are esterified with (meth)acrylic acid or homo- and copolymers of (meth)acrylates which are esterified with hydroxyalkyl(meth)acrylates.
The photopolymerisable compounds can be used by themselves or in any desired mixtures. It is preferred to use mixtures of polyol(meth)acrylates.
Binders may also be added to the compositions of the invention. The addition of binders is particularly useful if the photopolymerisable compounds are liquid or viscous substances.
The amount of binder may be from 5-95, preferably 10 -90 and, most preferably, 50-90, percent by weight, based on the entire composition. The choice of binder will depend on the field of use and the desired properties therefor, such as the ability of the compositions to be developed in aqueous and organic solvent systems, adhesion to substrates and susceptibility to oxygen.
Suitable binders are typically polymers having a molecular weight of about 5000-2 000 000, preferably 10 000-1000 000. Illustrative examples are: homo-and copolymers of acrylates and methacrylates, including copolymers of methyl meth-acrylate%thyl acrylate/methacrylic acid, poly(alkylmethacrylates), poly(alkylacrylates);
cellulose esters and ethers such as cellulose acetate, cellulose acetobutyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclised rubber, polyethers such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran;
polystyrene, polycarbonate, polyurethane, chlorinated polyolefms, polyvinyl chloride, copolymers of vinyl chloride/vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly(ethylene/vinyl acetate), polymers such as polycaprolactam and poly(hexamethylene adipamide), polyesters such as polyethylene glycol terephthalate) and poly(hexamethylene glycol succinate):
The unsaturated compounds can also be used in admixture with non-photopolymerisable film-forming components. These components may be physically drying polymers or solutions thereof in organic solvents, for example nitrocellulose or cellulose acetobutyrate.
They may, however, also be chemically or thermally curable resins such as polyiso-cynates, polyepoxides or melamine resins. The concurrent use of thermally curable resins is important for the use in so-called hybrid systems which, in a first step, are photopolymerised and, in a second step, crosslinked by a thermal aftertreatment.
y The photopolymerisable compositions of this invention conveniently contain the photoinitiator (b) in an amount of 0.05 to 15 % by weight, preferably of 0.2 to 5 % by weight, based on the composition.
The invention also relates to compositions which comprise, in addition to the photo-initiator (b), at least one further photoinitiator and/or other additives.
Further different additives which may be present in the photopolymerisable compositions in addition to the photoinitiator are typically thermal inhibitors which, especially during the preparation of the compositions by mixing the components, prevent premature poly-merisation. Such further additives are typically hydroquinone, hydroquinone derivatives, p-methoxyphenol, ~i-naphthol or sterically hindered phenols, such as 2,6-di(tert-butyl)-p-cresol.
To enhance storage stability in the dark it is possible to add copper compounds, including copper naphthenate, copper stearate or copper octoate, phosphorus compounds, including triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite, or tribenzyl phosphite, quaternary ammonium compounds, such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, such as N-diethyl-hydroxylamine.
The exclusion of atmospheric oxygen during the polymerisation may be effected by adding paraffin or similar wax-like substances which, at the onset of polymerisation, migrate to the surface owing to lack of solubility in the polymer and form a transparent film which prevents air from entering the system Minor amounts of UV absorbers, typically those of the benzotriazole, benzophenbne or oxanilide type, may be added as light stabilisers. Light stabilisers of the sterically hindered amine type (HALS) can also be added.
In specific cases it can be advantageous to use mixtures of two or more photoinitiators of this invention. Further photoinitiators used in addition to the photoinitiators of formula I
may be those selected from the following types: benzophenones, acetophenone derivatives, such as a-hydroxyalkylphenylketones, benzoin alkyl ethers and benzil ketals, or acyl phosphine oxides, bisacylphosphine oxides or titanocenes.
~~ ~, The photopolymerisation can be accelerated, especially in pigmented formulations, by adding amines, such as triethanolamine, N-methyl-diethanolamine, ethyl p-dimethyl-aminobenzoate or Michler's ketone. The action of the amines can be intensified by the addition of aromatic ketones of the benzophenone type.
The photopolymerisation can further be accelerated by the addition of photosensitisers which shift or broaden the spectral sensitivity. These photosensitisers are preferably aromatic carbonyl compounds such as benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives as well as 3-(aroylmethylene)thiazolines.
Depending on the envisaged end use further customary additives are fillers, pigments, dyes, adhesion promoters, wetting agents or levelling agents.
The photopolymerisable compositions can be used far a variety of purposes, including their use in printing ink compositions, in clear coating formulations, in white enamels, in paints, in paints for exterior coatings, and for photographic reproduction processes, for image recording processes or for the production of printing plates, for making three-dimensional objects, as by stereolithography or mass hardening, as dental filling compositions, as adhesives, as coatings for optical fibres, for printed electronic circuits or for coating electronic components.
In coating formulations there are frequently used two-component mixtures of a prepoly-mer with a polyunsaturated monomer or three-component mixtures which contain an addi-tional mono-unsaturated monomer. The prepolymer primarily determines the properties of the coat and, by varying it, the skilled person can influence the properties of the cured film. The polyunsaturated monomer acts as crosslinker which makes the coating film insoluble. The mono-unsaturated monomer acts as reactive diluent with the aid of which the viscosity is lowered without having to use a solvent.
Two- and three-component systems based on a prepolymer are used for printing inks as well as for coating compositions, photoresists or other photocurable compositions. Single component systems based on photocurable prepolymers are also often used as binders for printing inks.
Unsaturated polyester resins are normally used together with a mono-unsaturated ~a~~.j~.
monomer, preferably with styrene. Specific single component systems are often used for photoresists, for example the polymaleimides, polychalcones or polyimides disclosed in DE-OS 2 308 830.
The photocurable compositions of this invention may suitably be used as coating compositions for substrates of all kinds, such as wood, paper, ceramics, synthetic resins such as polyesters and cellulose acetate films, and metals such as copper and aluminium, to which it is desired to apply a protective layer or an image by photopolymerisation.
The substrate can be coated by applying to said substrate a liquid composition, a solution or suspension. This is done typically by dip-coating, brushing, spraying or reverse roller coating. The add-on (layer thickness) and the nature of the substrate (support) will depend on the desired field of application. Suitable substrates for reco~ing photographic information are sheets of polyester, cellulose acetate or resin-coated papers.
Specially treated aluminium is used for offset printing formes, and copper-clad laminates for making printed circuit boards. The layer thicknesses for photographic materials and offset printing formes are normally about 0.5 to about 10 Vim. If solvents are concurrently used, these can be removed after coating.
Photocuring is of great importance for printing inks, as the drying time of the binder is a decisive factor in the rate of production of graphic products and should be in the order of fractions of seconds. UV curable printing inks are of particular importance for screen printing.
The photocurable compositions of this invention are also very suitable for making printing plates. For this utility mixtures of soluble linear polyamides or styrene/butadiene rubber with photopolymerisable monomers, typically acrylamides, and a photoinitiator, are used.
Films and plates of these systems (wet or dry) are exposed via the negative (or positive) of the original and the non-cured parts are subsequently eluted with a solvent.
A further field of use of photocuring is metal coating, as in the coating of sheet metal and tubes, cans or bottle caps, as well as the photocuring of resin coatings, for example PVC
floor or wall coverings.
Illustrative of the photocuring of paper coatings is the colourless coating of labels, record sleeves or book jackets.
~a~j~~
The use of photocurable compositions is also important for imaging techniques and for the optical production of information carriers. For these utilities, the layer (wet or dry) applied to the substrate is irradiated through a photomask with shortwave light and the unexposed areas of the layer are removed by treatment with a solvent (= developer). The application of the photocurable layer can also be effected by electrodeposition on metal.
The exposed areas are crosslinked-polymeric and hence insoluble and remain on the substrate. Visible images are formed by appropriate colouration. If the substrate is a metallised layer, then the metal can be etched away after exposure and development at the unexposed areas or reinforced by galvanising. In this manner it is possible to make printed circuit boards and photoresists.
The invention further relates to a process for photopolymerising monomeric, oligomeric or polymeric compounds containing at least one ethylenically unsaturated double bond, which comprises adding to said compounds a compound of formula I and irradiating with light of wavelengths in the range from 200 to 600 nm.
Polymerisation is carried out by known methods of photopolymerisation by irradiation with sunlight or with light which is rich in shortwave radiation. Suitable light sources are typically mercury medium-pressure, high-pressure and low-pressure lamps, superactinic fluorescent tubes, metal halide lamps or lasers the maximum emissions of which are in the range from 250-450 nm. Laser light sources have the advantage that no photomasks are necessary, as the controlled laser beam writes direct onto the photocurable layer. Where combinations with photosensitisers are used, it is also possible to use light of longer wavelength or laser beams of up to 600 nm.
The compositions are conveniently prepared by mixing the individual components.
The invention further relates to a cured composition which is obtained by the above described process.
The bisacylphosphine sulfide photoinitiators of this invention have good solubility in conventional, preferably apolar, resins such as silicones.
A further advantage is the insignificant yellowing of the compositions cured with the inventive photoinitiators.
The invention is described in more detail by the following Examples in which and throughout the remainder of the description and in the claims, parts and percentages are by weight, unless otherwise indicated.
Example 1: Bis(2,6~iimethoxybenzoyl)-(2-methylpropyl)phosphine sulfide a) Bis(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphine A mixture of 5 ml (0.0425 mol) of (2-methylpropyl)phosphine and 13 ml (0.0935 mol) of triethylamine is added dropwise at 100-110 °C over 30 minutes to 18.8 g (0.0935 mol) of 2,6-dimethoxybenzoyl chloride in 100 ml of toluene. The reaction is brought to completion by stirring the reaction mixture at the same temperature for 6 hours, whereupon the product, as well as triethylammonium chloride, fall out as a yellowish precipitate. After cooling the reaction mixture, the ammonium salt is dissolved by addition of water and the product is isolated by filtration and dried under vacuum, affording 11.1 g (62.5 % of theory) of the title compound in the form of a white powder with a melting point of 138-140 °C.
Elemental analysis: C calcd: 63.15 % H calcd: 6.50 %
found: 63.19 % found: 6.52 %
b) Bis(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphine sulfide 10.0 g (0.024 mol) of bis(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphine are added to toluene and the mixture is heated to 60°C while introducing nitrogen, whereupon the educt dissolves completely. Then 0.8 g (0.024 mol) of sulfur are added at 60°C.The reaction mixture is thereafter stirred for 6 hours, cooled, and concentrated under vacuum. The residue is recrystallised from ethyl acetate, affording 6.9 g (63.9 % of theory) of the title compound in the form of a yellow powder with a melting point of 145-147°C.
Elemental analysis: calcd: C 58.6b % found: C 58.59 %
H 6.04% H 6.01%
S 7.12% S 7.03%
Examples 2-3: The compounds of Examples 2 and 3 are prepared using the appropriate starting phosphines in accordance with the general procedure described in Example 1.
O S O
I_II
R~
Table 1 ExampleRt Melting Elemental analysis point [%]
calcd. C H S
found 2 ~ 5 8.66 6.04 7.12 H 117-118 58.48 6.04 7.30 61.98 5.20 6.62 3 ~ ~
-CH2 138-139 61.88 5.25 6.83 Example 4: Initiator activity in a white enamel formulation A photopolymerisable composition comprising the following ingredients is prepared:
(the parts are parts by weight) 13.5 parts of ~Ebecryl 830 (polyester acrylate, UCB, Belgium) 0.5 part of trimethylolpropane trisacrylate (Degussa) 1 part of 1,6-hexanediol diacrylate (Rohm) 5.0 parts of titanium dioxide (rutile type; ~R-TC2 Tioxide, France) To this composition is added the amount of test photoinitiator given in Table 2. The formulation is applied in a layer thickness of 100 p,m to aluminium sheets.
The samples are then irradiated in a PPG exposure apparatus with mercury medium-pressure lamps (2 x 80 W/cm). The sample is passed under the lamps on a belt moving at a speed of m/min for as often as is necessary to obtain a wipe-resistant coating surface.
The fewer ~'~~~~.
the number of passes (n), the higher the reactivity of the tested compound.
The hardness of the sample is determined by means of the pendulum hardness test using the apparatus of Konig (DIN 53 157). The greater the number of seconds, the harder the tested sample. The yellowing of the sample is determined by measuring the Yellowness Index (YI) in accord-ance with ASTM D 1925-70. The lower the value, the lesser the yellowing of the sample.
The pendulum hardness and the yellowing are determined immediately after the cure and after an additional exposure for 15 minutes and 16 hours under 4 40 W Philips lamps.The gloss of the sample is measured in accordance with ASTM D 523 at an angle of incidence of 20° and 60° after an additional exposure of 15 minutes and 16 hours. The degree of reflected light is given in %. The higher the values, the better the gloss. The results are summarised in Table 2.
Table 2:
Compound Reactivity Pendulum hardnessYI Gloss 20/60 of [s]
Example [n x 10 immed. 15 min immed. 15 min [in %]
m/min] 16 h 16 h [wt. %]
1 % Ex. 6 106 157 181 1.7 0.3 -0.3 65/86 1 b 2 % Ex. 4 125 160 193 3.3 0.4 -0.2 78/90 1 b Example 5: Initiator reactivity in a white enamel formulation A photopolymerisable composition comprising the following ingredients is prepared:
30 % of ~Ebecryl 608 (epoxy acrylate, ex UCB, Belgium) 15 % of trimethylolpropane trisacrylate % of N-vinylpyrrolidone 50 % of titanium dioxide (rutile type; ~R-TC2; Tioxide, France) Two percent by weight of the photoinitiator of Example 1b) is incorporated in this formulation. The formulation is applied in a layer thickness of 100 p.m to an aluminium sheet. The 100 um layer is cured by irradiation with a Hanovia mercury medium-pressure lamp (80 W/cm). The sample is passed under the lamps on a belt moving at a speed of m/min for as often as is necessary to obtain a wipe-resistant coating surface.
The fewer the number of passes (n), the higher the reactivity of the tested compound.
The hardness of the sample is determined by means of the pendulum hardness test using the apparatus of Konig (DIN 53 157). The greater the number of seconds, the harder the tested sample. The ~p~ T /~
w ~~i~,~C~ .,~ Ate.
yellowing of the.sample is determined by measuring the Yellowness Index (YI) in accord-ance with ASTM D 1925-70. The lower the value, the lesser the yellowing of the sample.
The pendulum hardness and the yellowing are determined immediately after the cure and after an additional exposure for 15 minutes and 16 hours under 4 40 W Philips lamps.The gloss of the sample is measured in accordance with ASTM D 523 at an angle of incidence of 20° and 60° after an additional exposure of 15 minutes and 16 hours. The degree of reflected light is given in %. The higher the value, the better the gloss. The results are summarised in Table 3.
Table 3 Reactivity endulum YI Gloss hardness 20/60 [s] [in %]
[n x lOm/min]immed.15 16 immed.15 16 15 min 16 h min h min h 2 102 139 167 2.7 1.5 2.4 23/66 15/59
Also suitable for use as component (a) are the amides of identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines containing preferably 2 to 6, more particularly 2 to 4, amino groups. Exemplary of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-di-aminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, bis(~3-aminoethyl) ether, diethylenetriamine, triethylenetetramine, bis((3-aminoethoxy)ethane or bis((3-aminopropoxy)ethane. Other suitable polyamines are polymers and copolymers which may contain additional amino groups in the side-chain and oligoamides containing amino end groups.
Exemplary of such unsaturated amides are: methylenebisacrylamide, 1,6-hexamethylene-bisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)-ethane, (3-methacrylamidoethylmethacrylate, N-[((3-hydroxyethoxy)ethyl]acrylamide.
Suitable unsaturated polyesters and polyamides are derived typically from malefic acid and diols or diamines. Malefic acid can be partially replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, as with styrene. The polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from those with long chains containing typically from 6 to 20 carbon atoms. Polyurethanes are typically those derived from saturated or unsaturated diisocyanates and unsaturated and saturated diols.
Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers include olefins such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene or vinyl chloride. Polymers containing (meth)acrylate groups in the side-chain are _g_ also known. They may typically be reaction products of epoxy resins based on novolak with (meth)acrylic acid, homo- or copolymers of polyvinyl alcohol or their hydroxyalkyl derivatives which are esterified with (meth)acrylic acid or homo- and copolymers of (meth)acrylates which are esterified with hydroxyalkyl(meth)acrylates.
The photopolymerisable compounds can be used by themselves or in any desired mixtures. It is preferred to use mixtures of polyol(meth)acrylates.
Binders may also be added to the compositions of the invention. The addition of binders is particularly useful if the photopolymerisable compounds are liquid or viscous substances.
The amount of binder may be from 5-95, preferably 10 -90 and, most preferably, 50-90, percent by weight, based on the entire composition. The choice of binder will depend on the field of use and the desired properties therefor, such as the ability of the compositions to be developed in aqueous and organic solvent systems, adhesion to substrates and susceptibility to oxygen.
Suitable binders are typically polymers having a molecular weight of about 5000-2 000 000, preferably 10 000-1000 000. Illustrative examples are: homo-and copolymers of acrylates and methacrylates, including copolymers of methyl meth-acrylate%thyl acrylate/methacrylic acid, poly(alkylmethacrylates), poly(alkylacrylates);
cellulose esters and ethers such as cellulose acetate, cellulose acetobutyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclised rubber, polyethers such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran;
polystyrene, polycarbonate, polyurethane, chlorinated polyolefms, polyvinyl chloride, copolymers of vinyl chloride/vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly(ethylene/vinyl acetate), polymers such as polycaprolactam and poly(hexamethylene adipamide), polyesters such as polyethylene glycol terephthalate) and poly(hexamethylene glycol succinate):
The unsaturated compounds can also be used in admixture with non-photopolymerisable film-forming components. These components may be physically drying polymers or solutions thereof in organic solvents, for example nitrocellulose or cellulose acetobutyrate.
They may, however, also be chemically or thermally curable resins such as polyiso-cynates, polyepoxides or melamine resins. The concurrent use of thermally curable resins is important for the use in so-called hybrid systems which, in a first step, are photopolymerised and, in a second step, crosslinked by a thermal aftertreatment.
y The photopolymerisable compositions of this invention conveniently contain the photoinitiator (b) in an amount of 0.05 to 15 % by weight, preferably of 0.2 to 5 % by weight, based on the composition.
The invention also relates to compositions which comprise, in addition to the photo-initiator (b), at least one further photoinitiator and/or other additives.
Further different additives which may be present in the photopolymerisable compositions in addition to the photoinitiator are typically thermal inhibitors which, especially during the preparation of the compositions by mixing the components, prevent premature poly-merisation. Such further additives are typically hydroquinone, hydroquinone derivatives, p-methoxyphenol, ~i-naphthol or sterically hindered phenols, such as 2,6-di(tert-butyl)-p-cresol.
To enhance storage stability in the dark it is possible to add copper compounds, including copper naphthenate, copper stearate or copper octoate, phosphorus compounds, including triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite, or tribenzyl phosphite, quaternary ammonium compounds, such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, such as N-diethyl-hydroxylamine.
The exclusion of atmospheric oxygen during the polymerisation may be effected by adding paraffin or similar wax-like substances which, at the onset of polymerisation, migrate to the surface owing to lack of solubility in the polymer and form a transparent film which prevents air from entering the system Minor amounts of UV absorbers, typically those of the benzotriazole, benzophenbne or oxanilide type, may be added as light stabilisers. Light stabilisers of the sterically hindered amine type (HALS) can also be added.
In specific cases it can be advantageous to use mixtures of two or more photoinitiators of this invention. Further photoinitiators used in addition to the photoinitiators of formula I
may be those selected from the following types: benzophenones, acetophenone derivatives, such as a-hydroxyalkylphenylketones, benzoin alkyl ethers and benzil ketals, or acyl phosphine oxides, bisacylphosphine oxides or titanocenes.
~~ ~, The photopolymerisation can be accelerated, especially in pigmented formulations, by adding amines, such as triethanolamine, N-methyl-diethanolamine, ethyl p-dimethyl-aminobenzoate or Michler's ketone. The action of the amines can be intensified by the addition of aromatic ketones of the benzophenone type.
The photopolymerisation can further be accelerated by the addition of photosensitisers which shift or broaden the spectral sensitivity. These photosensitisers are preferably aromatic carbonyl compounds such as benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives as well as 3-(aroylmethylene)thiazolines.
Depending on the envisaged end use further customary additives are fillers, pigments, dyes, adhesion promoters, wetting agents or levelling agents.
The photopolymerisable compositions can be used far a variety of purposes, including their use in printing ink compositions, in clear coating formulations, in white enamels, in paints, in paints for exterior coatings, and for photographic reproduction processes, for image recording processes or for the production of printing plates, for making three-dimensional objects, as by stereolithography or mass hardening, as dental filling compositions, as adhesives, as coatings for optical fibres, for printed electronic circuits or for coating electronic components.
In coating formulations there are frequently used two-component mixtures of a prepoly-mer with a polyunsaturated monomer or three-component mixtures which contain an addi-tional mono-unsaturated monomer. The prepolymer primarily determines the properties of the coat and, by varying it, the skilled person can influence the properties of the cured film. The polyunsaturated monomer acts as crosslinker which makes the coating film insoluble. The mono-unsaturated monomer acts as reactive diluent with the aid of which the viscosity is lowered without having to use a solvent.
Two- and three-component systems based on a prepolymer are used for printing inks as well as for coating compositions, photoresists or other photocurable compositions. Single component systems based on photocurable prepolymers are also often used as binders for printing inks.
Unsaturated polyester resins are normally used together with a mono-unsaturated ~a~~.j~.
monomer, preferably with styrene. Specific single component systems are often used for photoresists, for example the polymaleimides, polychalcones or polyimides disclosed in DE-OS 2 308 830.
The photocurable compositions of this invention may suitably be used as coating compositions for substrates of all kinds, such as wood, paper, ceramics, synthetic resins such as polyesters and cellulose acetate films, and metals such as copper and aluminium, to which it is desired to apply a protective layer or an image by photopolymerisation.
The substrate can be coated by applying to said substrate a liquid composition, a solution or suspension. This is done typically by dip-coating, brushing, spraying or reverse roller coating. The add-on (layer thickness) and the nature of the substrate (support) will depend on the desired field of application. Suitable substrates for reco~ing photographic information are sheets of polyester, cellulose acetate or resin-coated papers.
Specially treated aluminium is used for offset printing formes, and copper-clad laminates for making printed circuit boards. The layer thicknesses for photographic materials and offset printing formes are normally about 0.5 to about 10 Vim. If solvents are concurrently used, these can be removed after coating.
Photocuring is of great importance for printing inks, as the drying time of the binder is a decisive factor in the rate of production of graphic products and should be in the order of fractions of seconds. UV curable printing inks are of particular importance for screen printing.
The photocurable compositions of this invention are also very suitable for making printing plates. For this utility mixtures of soluble linear polyamides or styrene/butadiene rubber with photopolymerisable monomers, typically acrylamides, and a photoinitiator, are used.
Films and plates of these systems (wet or dry) are exposed via the negative (or positive) of the original and the non-cured parts are subsequently eluted with a solvent.
A further field of use of photocuring is metal coating, as in the coating of sheet metal and tubes, cans or bottle caps, as well as the photocuring of resin coatings, for example PVC
floor or wall coverings.
Illustrative of the photocuring of paper coatings is the colourless coating of labels, record sleeves or book jackets.
~a~j~~
The use of photocurable compositions is also important for imaging techniques and for the optical production of information carriers. For these utilities, the layer (wet or dry) applied to the substrate is irradiated through a photomask with shortwave light and the unexposed areas of the layer are removed by treatment with a solvent (= developer). The application of the photocurable layer can also be effected by electrodeposition on metal.
The exposed areas are crosslinked-polymeric and hence insoluble and remain on the substrate. Visible images are formed by appropriate colouration. If the substrate is a metallised layer, then the metal can be etched away after exposure and development at the unexposed areas or reinforced by galvanising. In this manner it is possible to make printed circuit boards and photoresists.
The invention further relates to a process for photopolymerising monomeric, oligomeric or polymeric compounds containing at least one ethylenically unsaturated double bond, which comprises adding to said compounds a compound of formula I and irradiating with light of wavelengths in the range from 200 to 600 nm.
Polymerisation is carried out by known methods of photopolymerisation by irradiation with sunlight or with light which is rich in shortwave radiation. Suitable light sources are typically mercury medium-pressure, high-pressure and low-pressure lamps, superactinic fluorescent tubes, metal halide lamps or lasers the maximum emissions of which are in the range from 250-450 nm. Laser light sources have the advantage that no photomasks are necessary, as the controlled laser beam writes direct onto the photocurable layer. Where combinations with photosensitisers are used, it is also possible to use light of longer wavelength or laser beams of up to 600 nm.
The compositions are conveniently prepared by mixing the individual components.
The invention further relates to a cured composition which is obtained by the above described process.
The bisacylphosphine sulfide photoinitiators of this invention have good solubility in conventional, preferably apolar, resins such as silicones.
A further advantage is the insignificant yellowing of the compositions cured with the inventive photoinitiators.
The invention is described in more detail by the following Examples in which and throughout the remainder of the description and in the claims, parts and percentages are by weight, unless otherwise indicated.
Example 1: Bis(2,6~iimethoxybenzoyl)-(2-methylpropyl)phosphine sulfide a) Bis(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphine A mixture of 5 ml (0.0425 mol) of (2-methylpropyl)phosphine and 13 ml (0.0935 mol) of triethylamine is added dropwise at 100-110 °C over 30 minutes to 18.8 g (0.0935 mol) of 2,6-dimethoxybenzoyl chloride in 100 ml of toluene. The reaction is brought to completion by stirring the reaction mixture at the same temperature for 6 hours, whereupon the product, as well as triethylammonium chloride, fall out as a yellowish precipitate. After cooling the reaction mixture, the ammonium salt is dissolved by addition of water and the product is isolated by filtration and dried under vacuum, affording 11.1 g (62.5 % of theory) of the title compound in the form of a white powder with a melting point of 138-140 °C.
Elemental analysis: C calcd: 63.15 % H calcd: 6.50 %
found: 63.19 % found: 6.52 %
b) Bis(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphine sulfide 10.0 g (0.024 mol) of bis(2,6-dimethoxybenzoyl)-(2-methylpropyl)phosphine are added to toluene and the mixture is heated to 60°C while introducing nitrogen, whereupon the educt dissolves completely. Then 0.8 g (0.024 mol) of sulfur are added at 60°C.The reaction mixture is thereafter stirred for 6 hours, cooled, and concentrated under vacuum. The residue is recrystallised from ethyl acetate, affording 6.9 g (63.9 % of theory) of the title compound in the form of a yellow powder with a melting point of 145-147°C.
Elemental analysis: calcd: C 58.6b % found: C 58.59 %
H 6.04% H 6.01%
S 7.12% S 7.03%
Examples 2-3: The compounds of Examples 2 and 3 are prepared using the appropriate starting phosphines in accordance with the general procedure described in Example 1.
O S O
I_II
R~
Table 1 ExampleRt Melting Elemental analysis point [%]
calcd. C H S
found 2 ~ 5 8.66 6.04 7.12 H 117-118 58.48 6.04 7.30 61.98 5.20 6.62 3 ~ ~
-CH2 138-139 61.88 5.25 6.83 Example 4: Initiator activity in a white enamel formulation A photopolymerisable composition comprising the following ingredients is prepared:
(the parts are parts by weight) 13.5 parts of ~Ebecryl 830 (polyester acrylate, UCB, Belgium) 0.5 part of trimethylolpropane trisacrylate (Degussa) 1 part of 1,6-hexanediol diacrylate (Rohm) 5.0 parts of titanium dioxide (rutile type; ~R-TC2 Tioxide, France) To this composition is added the amount of test photoinitiator given in Table 2. The formulation is applied in a layer thickness of 100 p,m to aluminium sheets.
The samples are then irradiated in a PPG exposure apparatus with mercury medium-pressure lamps (2 x 80 W/cm). The sample is passed under the lamps on a belt moving at a speed of m/min for as often as is necessary to obtain a wipe-resistant coating surface.
The fewer ~'~~~~.
the number of passes (n), the higher the reactivity of the tested compound.
The hardness of the sample is determined by means of the pendulum hardness test using the apparatus of Konig (DIN 53 157). The greater the number of seconds, the harder the tested sample. The yellowing of the sample is determined by measuring the Yellowness Index (YI) in accord-ance with ASTM D 1925-70. The lower the value, the lesser the yellowing of the sample.
The pendulum hardness and the yellowing are determined immediately after the cure and after an additional exposure for 15 minutes and 16 hours under 4 40 W Philips lamps.The gloss of the sample is measured in accordance with ASTM D 523 at an angle of incidence of 20° and 60° after an additional exposure of 15 minutes and 16 hours. The degree of reflected light is given in %. The higher the values, the better the gloss. The results are summarised in Table 2.
Table 2:
Compound Reactivity Pendulum hardnessYI Gloss 20/60 of [s]
Example [n x 10 immed. 15 min immed. 15 min [in %]
m/min] 16 h 16 h [wt. %]
1 % Ex. 6 106 157 181 1.7 0.3 -0.3 65/86 1 b 2 % Ex. 4 125 160 193 3.3 0.4 -0.2 78/90 1 b Example 5: Initiator reactivity in a white enamel formulation A photopolymerisable composition comprising the following ingredients is prepared:
30 % of ~Ebecryl 608 (epoxy acrylate, ex UCB, Belgium) 15 % of trimethylolpropane trisacrylate % of N-vinylpyrrolidone 50 % of titanium dioxide (rutile type; ~R-TC2; Tioxide, France) Two percent by weight of the photoinitiator of Example 1b) is incorporated in this formulation. The formulation is applied in a layer thickness of 100 p.m to an aluminium sheet. The 100 um layer is cured by irradiation with a Hanovia mercury medium-pressure lamp (80 W/cm). The sample is passed under the lamps on a belt moving at a speed of m/min for as often as is necessary to obtain a wipe-resistant coating surface.
The fewer the number of passes (n), the higher the reactivity of the tested compound.
The hardness of the sample is determined by means of the pendulum hardness test using the apparatus of Konig (DIN 53 157). The greater the number of seconds, the harder the tested sample. The ~p~ T /~
w ~~i~,~C~ .,~ Ate.
yellowing of the.sample is determined by measuring the Yellowness Index (YI) in accord-ance with ASTM D 1925-70. The lower the value, the lesser the yellowing of the sample.
The pendulum hardness and the yellowing are determined immediately after the cure and after an additional exposure for 15 minutes and 16 hours under 4 40 W Philips lamps.The gloss of the sample is measured in accordance with ASTM D 523 at an angle of incidence of 20° and 60° after an additional exposure of 15 minutes and 16 hours. The degree of reflected light is given in %. The higher the value, the better the gloss. The results are summarised in Table 3.
Table 3 Reactivity endulum YI Gloss hardness 20/60 [s] [in %]
[n x lOm/min]immed.15 16 immed.15 16 15 min 16 h min h min h 2 102 139 167 2.7 1.5 2.4 23/66 15/59
Claims (15)
1. A compound of formula I
wherein R1 is unsubstituted C1-C18alkyl or C1-C8alkyl which is substituted by phenyl, -CN, C1-C12alkoxy or halogen, C2-C18alkenyl; unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C12alkoxy or halogen, unsubstituted C6-C12aryl or C6-C12aryl which is substituted by halogen, C1-C12alkyl or C1-C12alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted C1-C18alkyl or C1t-C8alkyl which is substituted by phenyl, halogen or C1-C12alkoxy, C2-C6alkenyl, unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C12alkoxy or halogen, unsubstituted C6-C12aryl or C6-C12aryl which is substituted by C1-C12alkyl, C1-C12alkoxy, C2-C12alkoxyalkyl, C1-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy.
wherein R1 is unsubstituted C1-C18alkyl or C1-C8alkyl which is substituted by phenyl, -CN, C1-C12alkoxy or halogen, C2-C18alkenyl; unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C12alkoxy or halogen, unsubstituted C6-C12aryl or C6-C12aryl which is substituted by halogen, C1-C12alkyl or C1-C12alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted C1-C18alkyl or C1t-C8alkyl which is substituted by phenyl, halogen or C1-C12alkoxy, C2-C6alkenyl, unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C12alkoxy or halogen, unsubstituted C6-C12aryl or C6-C12aryl which is substituted by C1-C12alkyl, C1-C12alkoxy, C2-C12alkoxyalkyl, C1-C4alkylthio or halogen, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy.
2. A compound according to claim 1, wherein R1 is unsubstituted C1-C12alkyl or C1-C8alkyl which is substituted by phenyl; -CN, C1-C4alkoxy or halogen, C2-C12alkenyl, unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C4alkoxy or halogen, unsubstituted C6-C12aryl or C6-C12ary1 which is substituted by halogen, C1-C12alkyl or C1-C4alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy, and R1 and R3 are each independently of the other unsubstituted C1-C12alkyl or C1-C8alkyl which is substituted by phenyl, halogen or C1-C4alkoxy, C2-C6alkenyl, unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C4alkoxy or halogen, unsubstituted C6-C12aryl or C6-C12aryl which is substituted by C1-C12alkyl, C1-C4alkoxy, C2-C8alkoxyalkyl, C1-C4alkylthio or halogen, or a 5-or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C1-C4alkyl or C1-C4alkoxy.
3. A compound according to claim 2, wherein R1 is unsubstituted C1-C12alkyl or C1-C4alkyl which is substituted by phenyl, -CN, C1-C4alkoxy or halogen, C2-C6alkenyl, or unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C4alkoxy or halogen, or unsubstituted C6-C12aryl or C6-C12aryl which is substituted by halogen, C1-C12alkyl or C1-C12alkoxy, and R2 and R3 are each independently of the other unsubstituted C1-C12alkyl or C1-C4alky1 which is substituted by phenyl, halogen or C1-C4alkoxy, C2-C6alkenyl, or unsubstituted C5-C8cycloalkyl or C5-C8cycloalkyl which is substituted by C1-C12alkyl, C1-C4alkoxy or halogen, or unsubstituted C6-C12aryl or C6-C12aryl which is substituted by C1-C12alkyl, C1-C4alkoxy, C2-C8alkoxyalkyl, C1-C4alkylthio or halogen.
4. A compound according to claim 3, wherein R1 is unsubstituted C1-C12alkyl, phenyl-C1-C4alkyl, unsubstituted or C1-C12alkyl-substituted cyclopentyl or cyclohexyl, or unsubstituted phenyl or phenyl which is substituted by halogen, C1-C12alkyl or C1-C4alkoxy, and R2 and R3 are each independently of the other unsubstituted C1-C12alkyl, phenyl-C1-C4alkyl, unsubstituted or C1-C12alkyl-substituted cyclopentyl or cyclohexyl, or unsubstituted phenyl or phenyl which is substituted by C1-C12alkyl, C1-C4alkoxy or halogen.
5. A compound according to claim 4, wherein R1 is C1-C12alkyl, cyclohexyl or phenyl-C1-C4alkyl, and R2 and R3 an each independently of the other phenyl which is substituted by C1-C4alkoxy, halogen or C1-C4alkyl.
6. A compound according to any one of claims 1 to 5, wherein R2 and R3 are identical.
7. A compound according to claim 6, wherein R1 is C1-C8alkyl or benzyl, R2 and R3 are C1-C4alkyl- or C1-C4alkoxy-substituted phenyl.
8. A composition comprising (a) at least one ethylenically unsaturated photopolymerisable compound and (b) as photoinitiator at least one compound of formula I, according to any one of claims 1 to 7.
9. A composition according to claim 8 which, in addition to the photoinitiator compound (b), comprises at least one further photoinitiator and/or other additives
10. A composition according to claim 8 comprising 0.05 to 15% by weight of component b), based on said composition.
11. A composition according to claim 10 comprising 0.2 to 5% by weight, of component b), based on said composition.
12. A process for photopolymerising compounds containing ethylenically unsaturated double bonds, which comprises irradiating a composition as claimed in any one of claims 8 to 11 with light in the range from 200 to 600 nm.
13. A process according to claim 12 for the preparation of coating compositions, composites, printing plates, photoresists for electronic printed circuits, adhesives or coatings for optical fibres.
14. A process according to claim 12, which is carried out according to the method of mass curing or stereolithography.
15. A curd composition obtained by the process as claimed in claim 12.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH8491 | 1991-01-14 | ||
CH84/91-2 | 1991-01-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2059144A1 CA2059144A1 (en) | 1992-07-15 |
CA2059144C true CA2059144C (en) | 2002-07-16 |
Family
ID=4178903
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2059144 Expired - Fee Related CA2059144C (en) | 1991-01-14 | 1992-01-10 | Bisacylphosphine sulfides |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0495752B1 (en) |
JP (1) | JP3203431B2 (en) |
CA (1) | CA2059144C (en) |
DE (1) | DE59201477D1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2091385C1 (en) * | 1991-09-23 | 1997-09-27 | Циба-Гейги АГ | Bisacylphosphine oxides, composition and method of application of coatings |
ES2059261B1 (en) * | 1992-10-08 | 1995-11-16 | Ciba Geigy Ag | ALKYL-BISACILPHOSPHINOXIDES. |
CA2134156A1 (en) * | 1993-11-22 | 1995-05-23 | Thomas P. Klun | Coatable compositions, abrasive articles made therefrom, and methods of making and using same |
TW303379B (en) * | 1994-03-02 | 1997-04-21 | Ciba Sc Holding Ag | |
WO1996007662A1 (en) * | 1994-09-08 | 1996-03-14 | Ciba Specialty Chemicals Holding Inc. | Novel acylphosphine oxides |
WO1997009168A1 (en) * | 1995-09-09 | 1997-03-13 | Zeneca Limited | Process for producing polymeric layers having selectively coloured regions |
US6130980A (en) * | 1997-05-06 | 2000-10-10 | Dsm N.V. | Ribbon assemblies and ink coating compositions for use in forming the ribbon assemblies |
ES2230654T3 (en) * | 1998-11-11 | 2005-05-01 | Minnesota Mining And Manufacturing Company | MULTI PAPER SHEET THAT INCLUDES A POLYURETHANE PROTECTIVE COAT |
GB2365430B (en) * | 2000-06-08 | 2002-08-28 | Ciba Sc Holding Ag | Acylphosphine photoinitiators and intermediates |
EP1423757B1 (en) | 2001-08-21 | 2009-04-29 | Ciba Holding Inc. | Bathochromic mono- and bis-acylphosphine oxides and sulfides and their use as photoinitiators |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3034697A1 (en) * | 1980-09-15 | 1982-05-06 | Basf Ag, 6700 Ludwigshafen | ACYLPHOSPHINE SULFIDE COMPOUNDS, THEIR PRODUCTION AND USE |
DE3443221A1 (en) * | 1984-11-27 | 1986-06-05 | ESPE Fabrik pharmazeutischer Präparate GmbH, 8031 Seefeld | BISACYLPHOSPHINOXIDE, THEIR PRODUCTION AND USE |
-
1992
- 1992-01-07 DE DE59201477T patent/DE59201477D1/en not_active Expired - Fee Related
- 1992-01-07 EP EP19920810006 patent/EP0495752B1/en not_active Expired - Lifetime
- 1992-01-10 CA CA 2059144 patent/CA2059144C/en not_active Expired - Fee Related
- 1992-01-14 JP JP02463592A patent/JP3203431B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH0586080A (en) | 1993-04-06 |
JP3203431B2 (en) | 2001-08-27 |
DE59201477D1 (en) | 1995-04-06 |
EP0495752A1 (en) | 1992-07-22 |
EP0495752B1 (en) | 1995-03-01 |
CA2059144A1 (en) | 1992-07-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2059145A1 (en) | Bisacylphosphines | |
KR100363978B1 (en) | Alkoxyphenyl-substituted bisacylphosphine oxides | |
US6284813B1 (en) | Alkylphenylbisacylphosphine oxides and photoinitiator mixtures | |
US6486228B2 (en) | Mono-and Bis-acylphosphine oxide photoinitiator combinations | |
US6737549B2 (en) | Organometallic monoacylalkylphosphines | |
US5399770A (en) | Alkylbisacylphosphine oxides | |
KR100358815B1 (en) | Dimeric bisacylphosphines, oxides and sulfide compounds and compositions comprising these compounds | |
US6361925B1 (en) | Photoinitiator mixtures and compositions with alkylphenylbisacylphosphine oxides | |
CA2059144C (en) | Bisacylphosphine sulfides | |
AU682793B2 (en) | Novel acylphosphine oxides | |
US5399782A (en) | Benzoyl-substituted phosphabicycloalkanes and phosphabicycloalkanesulfides as photoinitiators | |
US5368985A (en) | Bisacylphosphine sulfides | |
US5210110A (en) | Silylated acylphosphine oxides | |
KR20000047902A (en) | Photoinitiator combinations |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |