WO2009155425A1 - Photochromic coating exhibiting improved performance and reduced yellowness - Google Patents
Photochromic coating exhibiting improved performance and reduced yellowness Download PDFInfo
- Publication number
- WO2009155425A1 WO2009155425A1 PCT/US2009/047806 US2009047806W WO2009155425A1 WO 2009155425 A1 WO2009155425 A1 WO 2009155425A1 US 2009047806 W US2009047806 W US 2009047806W WO 2009155425 A1 WO2009155425 A1 WO 2009155425A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- photochromic
- amount
- phm
- meth
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 230000002829 reductive effect Effects 0.000 title claims abstract description 7
- 230000001747 exhibiting effect Effects 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 239000000178 monomer Substances 0.000 claims abstract description 43
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 41
- 150000003254 radicals Chemical class 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 239000008199 coating composition Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 239000004611 light stabiliser Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 24
- -1 bismuth carboxylate Chemical class 0.000 claims description 23
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 12
- 150000001451 organic peroxides Chemical class 0.000 claims description 12
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 9
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 8
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 8
- 229940091853 isobornyl acrylate Drugs 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
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- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 5
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- 125000005474 octanoate group Chemical group 0.000 claims description 2
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 claims description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims 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 claims 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims 1
- MCRZWYDXIGCFKO-UHFFFAOYSA-N 2-butylpropanedioic acid Chemical compound CCCCC(C(O)=O)C(O)=O MCRZWYDXIGCFKO-UHFFFAOYSA-N 0.000 claims 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
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- 229920000515 polycarbonate Polymers 0.000 description 17
- 239000004417 polycarbonate Substances 0.000 description 17
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 15
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- 125000003003 spiro group Chemical group 0.000 description 11
- YGFLYIFQVUCTCU-UHFFFAOYSA-N 2-ethylhexoxy 2-methylbutan-2-yl carbonate Chemical compound CCCCC(CC)COOC(=O)OC(C)(C)CC YGFLYIFQVUCTCU-UHFFFAOYSA-N 0.000 description 9
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 7
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 7
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000010504 bond cleavage reaction Methods 0.000 description 6
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexanol Substances CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 5
- BRQMAAFGEXNUOL-LLVKDONJSA-N [(2R)-2-ethylhexyl] (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCC[C@@H](CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-LLVKDONJSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 4
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- ZLRFPQPVXRIBCQ-UHFFFAOYSA-N 2-$l^{1}-oxidanyl-2-methylpropane Chemical compound CC(C)(C)[O] ZLRFPQPVXRIBCQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- FAQVDANXTSFXGA-UHFFFAOYSA-N 2,3-dihydro-1h-benzo[g]indole Chemical compound C1=CC=CC2=C(NCC3)C3=CC=C21 FAQVDANXTSFXGA-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
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- 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
- 239000000973 cosmetic coloring agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000005534 decanoate group Chemical class 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- UKRVECBFDMVBPU-UHFFFAOYSA-N ethyl 3-oxoheptanoate Chemical compound CCCCC(=O)CC(=O)OCC UKRVECBFDMVBPU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical class CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- KNMWLFKLSYMSBR-UHFFFAOYSA-N iron;octanoic acid Chemical compound [Fe].CCCCCCCC(O)=O KNMWLFKLSYMSBR-UHFFFAOYSA-N 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- GSZRRTSGQIIDKS-UHFFFAOYSA-M lithium;7,7-dimethyloctanoate Chemical compound [Li+].CC(C)(C)CCCCCC([O-])=O GSZRRTSGQIIDKS-UHFFFAOYSA-M 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- KQSJSRIUULBTSE-UHFFFAOYSA-M sodium;3-(3-ethylcyclopentyl)propanoate Chemical compound [Na+].CCC1CCC(CCC([O-])=O)C1 KQSJSRIUULBTSE-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Eyeglasses (AREA)
- Optical Filters (AREA)
Abstract
An acrylate-based optical coating composition containing a blend of monomers, a metal salt, a Hindered Amine Light Stabilizer (HALS), an antioxidant (AO), an initiator and a photochromic dye. The initiator has a range of free radical energy that is below a predetermined level. The cure process is controlled by the catalyst and initiator in combination with the HALS and AO to avoid deleterious reactions that can increase yellowness. The composition is well suited to be applied to a lens and cured in the mold to form a coating with reduced yellowness having high adhesion and abrasion-resistant properties. A photochromic segmented bifocal lens is produced with low photochromic fatigue and favorable %T values.
Description
PHOTOCHROMIC COATING EXHIBITING IMPROVED PERFORMANCE AND REDUCED YELLOWNESS
BACKGROUND OF THE INVENTION 1 , Field of the Invention
The invention relates to a photochromic coating and to a method for making a photochromic polycarbonate lens using the coating. More particularly, the composition is applied to a lens and cured in the mold to form a coating with reduced yellowness having high adhesion and abrasion-resistance. The coaling will exhibit excellent photochromic darkening and fatigue properties,
2. Description of the Related Art
Injection molded polycarbonate ophthalmic lenses are lightweight and possess excellent mechanical properties, Photochromic dyes are incorporated into certain lenses to enhance their optical properties by automatically lightening or darkening based on the amount and type of light that they receive. Since the photochromic dye molecules can decompose when exposed to the heat of the injection molding process, such dyes need to be introduced on to the lens after the injection molding step. One method is to incorporate the photochromic dye into a coating composition and apply it to a lens surface via dip coating or spin coating. The surface discontinuity of bifocal and trifocal segmented lenses are not well suited to these typical coating processes. The viscous coating material builds-up at the segment which results in an undesirable darker color at the segment when exposed to UV light. A prior art process utilizing a photochromic polyurethane coating is shown in U.S. Patent 6,187,444 and U.S. Patent 7,258,437, These approaches do not use organic peroxides in the coating compositions, rather they utilize condensation reactions.
Photochromic (PhCh) semi-finished straight-top SFST lenses can be made by injection molding polycarbonate (PC) behind a photochromic wafer. The wafer can be a tri-iayer of PC/PhCh/PC. VisionEase U.S. Patent 7,036,932 and U.S. Published Patent Application 2007/0122626 describes such a product.
Another method is to overmold a bifocal on top of a lens as described in US Pat
7,258,437. Generally, the overmold casting solution is not photo chromic, as mentioned in U.S. Patent 5,531,940, with the lens optionally containing photochromies. As described in U.S. Patent 5,531,940 and JP Appl. 2004-076411 the overmolding solution can contain photochromic materials and the lens can be non-photo chromic, or a combination of the two. The overmold solution can be cured by either UV, thermal or a combination of each, for example as described in U.S. Patent 6,863,844, U.S. Patent
6,602,603 and U.S. Patent 5,621,017. With these ensembles the desirable high impact nature of the polycarbonate can be compromised because the overmold layer replaces a portion of the total lens thickness.
With the current methods of depositing viscous urethane photochromic coatings as described in U.S. Patent 7,189,456, it is extremely difficult, if not impossible, to produce a polycarbonate photochromic semi-finished segmented {bifocal or trifocal) optical lens. The viscous coating material will build-up at the segment which results in an undesirable darker color at the segment when exposed to UV light. Other such photochromic coatings are Aminoplast melamine PhCh coatings, mentioned in U.S. Patents 6,506,488 and 6,432,544. Thermal initiators are used to prepare polymers, while acid catalysts (eg. p-TSA) cure the photochromic Cymel resin mixture. A photochromic epoxy coating is described in U.S. Patent 6,268,055. Thermal initiators are only used to prepare the polymers, no peroxidic initiator is used to cure the epoxy PhCh coating.
Another method is proposed in U.S. Published Patent AppHcatin 2007/0138665 where a polycarbonate lens substrate is injection molded. The mold block opens and a few drops of a coating liquid are applied to the front surface of the polycarbonate lens. The mold block then closes. This serves two (2) purposes. First, when the mold block closes, it spreads the coating over the front (CX) surface of the polycarbonate lens to provide a uniform thickness. Secondly, the mold block will provide suitable heat to cure the coaling formulation. When the coating is a photochromic coating, the organic peroxide thermal initiator (t-butylperoxybenzoate) appears to damages the photochromic molecules resulting in a visible yellow color.
Accordingly, there is a need to produce coatings with low yellow color. More particularly, it would be desixeable to provide a photochromic coating composition with
reduced yellowness, and a method for in-mold coating, especially for coating bifocal or trifocal segmented lenses.
In addition, there is a need for a photo chromic coating formulation and application method which will result in good lens transparency, a high level of pholochromic performance and minimal photochromic fatigue.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide a coating composition and in- mold coating process that provides a cured coating with low yellowness.
It is a further object to control the curing process to minimize molecular degradation through careful selection of an organic peroxide initiator.
It is another object to provide a photochromic coating composition in which the photochromic molecules remain intact and are not damaged during the curing process.
It is yet a further object to identify a range of radical energy levels associated with the initiators that achieves a fast cure times without negatively interacting with other compounds.
It is another object of the invention to specify organic peroxide initiators having a radical energy level below about 113 kcal/mol.
It is an object of the present invention to provide a photochromic coating which exhibits improved photochromic performance.
It is another object to provide a coating that has minimal photochromic fatigue.
It is yet a further object to provide a photochromic coating which is suitable for use in an in-mold coating process.
Il is another object to provide a suitably coated photochromic bifocal lens.
These and other related objects according to one embodiment of the invention are achieved by a thermally curable photochromic coating composition comprising a metal salt catalyst; a Hindered Amine Light Stabilizer (HALS); an antioxidant; an initiator; a photochromic dye; and a mixture having two different monomers. The monomers are selected from the group consisting of: (a) monofunctional (meth)acrylate; (b) difunctional (meth)acrylate; (c) a combination of a monofunctional (meth)acrylate and a
difunctional (meth)acrylate; (d) multifunctional (meth)acrylate; and (e) aliphatic urethane diacrylate.
According to a further embodiment, there is provided a method for manufacturing an injection molded thermoplastic photochromic bifocal lens. Initially, there is provided an acrylate-based photochromic coating composition including two different types of monomers, a metal salt catalyst, a Hindered Amine Light Stabilizer (HALS), an antioxidant, an initiator and a photochromic dye. Next molten thermoplastic is injected into an edge-gated bifocal-lens forming cavity of an injection molding machine to provide a bifocal lens substrate. The mold is opened at a time when the bifocal lens is rigid enough to retain its shape, The photochromic composition is applied onto the bifocal lens substrate. Next, the mold is closed to spread the photochromic composition into a uniformly thin layer so that residual heat from the molding machine cures the photochromic composition into a coating with low photochromic fatigue and reduced yellowing. The photochromic coating is applied across a segmented surface of the bifocal lens to a thickness in the range from about 1 to 10 μm, and wherein the photochromic fatigue is less than 15% and the %T dark is less than 16%.
The HALS is [4-(methoxyphenyl)-methylene]-bis-l,2,2,6,6-pentamethyl-4- piperidinyl-propanedioic acid ester or bis (l^^^ό-pentamethyM-piperidinylH^S- bis-(l,l-dimethylethyl)-4-hydroxyphenyl]methyl]butyhualonate. The antioxidant is a sterically hindered phenolic compound and preferably a pentaerythritol tetrakis[3-(3,5- di~tert-butyl-4-hydroxyphenyl)propionate]hindered phenolic compound. The initiator is an organic peroxide which presents a free radical energy less than about 113 kcal/mol at 298 K, preferably t-amylperoxy-2-ethylhexyl carbonate organic peroxide or t- butylperoxy-2-ethylhexyIc arbonate.
In a coating according another embodiment, the monomers of (a) monofunctional
(meth)acrylate; (b) difunctional (meth)acrylate; and (c) a combination of a monofunctional (meth)acrylate and a difunctional (meth)acrylate are present in an amount from 10% to 25% by weight. The monomers of (d) multifunctional (meth) aery] ate are present in an amount from 20% to 40% by weight. The monomers of (e) aliphatic urethane diacrylate are present in an amount from 50% to 70% by weight. The metal salt is present in an amount from 0, 10 phm to 0.30 phm. The Hindered amine light stabilizer (HALS) is present in an amount from 1.00 phm to 5.00 phm. The
antioxidant is present in an amount from 0.20 phm to 0.50 phm. The initiator is present in an amount from 1.00 phm to 2.00 phm and the photochromic dye is presents in an amount from 2.00 phm to 5.00 phm.
In a coating according to a further embodiment, the mixture of monomers includes isobornylacrylate present in an amount of 5% by weight, hydroxypropylmethacrylate preferably HPMA present in an amount of 10% by weight, aliphatic urethane diacrylate present in an amount of 18% by weight, hexafunctional aliphatic urethane acrylate present in an amount of 33% by weight, and aliphatic urethane diacrylate present in an amount of 34% by weight. The metal salt is tin-2- ethylhexanoate present in an amount of 0.14 phm. The Hindered amine light stabilizer (HALS) comprises bis (l^^.βsβ-pentamerayM-piperidinylHfS.S-bis-ζl,-- dimethylethyl)-4-hydroxyphenyl]metbyl]butyhnalonate present in an amount of 1 phm. The antioxidant comprises pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- hydτoxyphenyl)propionate]hindered phenolic compound present in an amount of 0.25 phm. The initiator comprises t-amylperoxy-2-elhylhexyl carbonate organic peroxide present in an amount of 1.5 phm and the photochromic dye is present in an amount of 0.25 phm.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages, nature, and various additional features of the invention will appear more fully upon consideration of the illustrative embodiments now to be described in detail in connection with accompanying drawings. In the drawings:
FIG. 1 is a flowchart outlining the steps for an in-mold application of an acrylate- based coating to manufacture a photochromic lens with low yellowness.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Thermoplastic lenses must be extremely clean before they can be coated. In the regular lens coating process, after the lenses are taken out of mold and degated, they have to be transferred and go through several different cleaning tanks before being coated, The coatings often require heat or UV light in order to cure. The transfer, cleaning, coating and curing operations utilize vast amounts of space and have high power demands to operate conveyors, pumps, heaters and curing ovens. That adds to the cost of the finished product. Accordingly, it would be desirable to coat a lens soon after it is formed by injection molding. In contrast to the prior art, a lens can be coated in- mold within 1 or 2 minutes of initial environmental contact before ejection or degating, thereby eliminating those operations as contamination sources.
According to one embodiment of the invention, a photochromic coating formulation is provided. The coating formulation contains (1) a photochromic dye; (2) an antioxidant (AO); (3) a metal salt catalyst; (4) an initiator; (5) a hindered amine light stabilizer (HALS), and (6) a blend of monomers.
An embodiment of the lens coating process according to the invention will be characterized by the following steps. In the cooling stage of the lens molding, the mold will open for coating deposition. The mold can open as soon as the lens substrate is rigid enough to sustain mold opening. That is, the lens shape which determines the degree of aberration and power, will resist deformation under mold depressurization and vacuum forces. The coating is deposited as an unpressurized coating solution onto the lens substrate. The mold is reclamped to contact the coating with the upper mold insert and spread an even layer over the lens surface. The coating spread pressure is directed in exactly the same direction and manner as the lens forming clamp pressure. Once closed the coating is heated from below by the lens substrate, and from above by the mold insert. A 1-5 minute coating cure phase is provided while the lens achieves sufficient solidification to be ejected from injection molding machine.
According to one embodiment of the invention, our proposed solution is to utilize the above noted process with a coating composition containing a dye(s) and an organic peroxide and a metal catalyst. A thermal initiator will be chosen that provides a tinted coating with minimal yellow color, and wherein the tint could be choosen from cosmetic
dyes, tint dyes, photochromic dyes, dichroic dyes and combination thereof , More specifically, per step 12, the initiator is an organic peroxide class material having a radical energy that is lower than about 113 kcal/mol at 298 degrees K. The coating composition is formulated in step 10 and may optionally contain an optical dye. Such a composition produces, after ejection from the injection molding machine, a semifinished lens wherein the convex side is provided with a coating without a yellow color defect. A complete description of the composition components and examples of particular coating formulations will now be presented.
Organic peroxides are known initiators for acrylic monomers. Initiators contain one or more labile bonds that cleave homolytically when sufficient energy is supplied to the molecule. The energy must be greater than the bond dissociation energy (BDE) of the labile bond, as described in the Kirk-Othmer Encyclopedia of Chemical Technology. Energetic free radicals are formed during thermal decomposition of the organic peroxide. Metal catalysts such as cobalt naphthenate are known accelerators that will speed up the cure or ensure a more efficient conversion of monomer to polymer. These energetic free radicals are known to abstract hydrogen, attack unsaturations or interact with stabilizers. Other times, it is desireable to avoid attack to additives such as photochromic materials.
The thermal decomposition or thermolysis mechanism for a particular peroxide depends upon the molecular structure, primarily electronic and steric effects. The radical's ability to exist is based on its stability as a radical. For example, if the peroxide is stable at room temperature, it prefers to exist as the peroxide molecule. A peroxide that is refrigerated prefers to decompose to the radical, the radical is the lower energy state.
As the bond dissociation energy decreases, the radical stability increases. To abstract a hydrogen from a benzene molecule would require 113.1 Kcal/mol. The radical is highly energetic and unstable. Whereas to abstract a hydrogen from a t-butyl molecule is much lower at 96.6 Kcal/mol, so the radical has less energy (softer) and it is more likely to be able to abstract this hydrogen. A list of Relative Radical Stabilities is shown in Table 1, in which certain values are cited from the Handbook of Chemistry & Physics, 81sl Ed. or were provided by Arkema Inc..
Table 1
Structure Bond Dissociation Energy Radical
Ocoal/molei at 298K creasing radical energy
Table 1 is organized to show increasing radical stability (decreasing radical energy) as one moves down the listing. The thermal decompositon of some initiators used are shown,
Luperox P: (t-butylperoxybenzoate)
T-butylperoxybenzoate (Luperox PJ thermal decomposition is described in the Arkema
Peroxyesters Product Bulletin as among the commercial peroxyesters of peroxybenzoic acids to decompose by a mechanism that initially gives acyloxy and alkoxy radicals, after which decarboxylation or β-scission often occurs, T-butylperoxybenzoate decomposes into a benzoyloxy radical and a t-butoxy radical.
O O
I! Il
C6H5-C-OO- -^C4H9 ^ C6H5-C-O - + .0— f-GjHg
The benzoyloxy can further decarboxylate kirietically to a higher energy phenyl radical (113.2 Kcal/mol) and carbon dioxide.
O Il C6H5-C-O. (106.1 Kcal/mol) 4s C6H5 * (113.1 Kcal/mol) + CO2
While the t-bntoxy radical (105.1KcalΛnol) may further decompose by β-scission to a methyl radical (104.9KCaVmOl)1 it would be a very slow reaction as the driving force is low with ΔH=0.2 Kcal/mol.
O slow Il
C(CH3J3^O • (105.1Kcal/mol) ■* CH3- (104.9Kcal/mol) + CH3-C-CH3
Luperox TAEC: OO-t-amyl-O-fl-ethylhexyDmonopcroxycarbonate ft-amylperoxy- 2-ethylhexylcarbonate)
00-t-amyl-0-(2-ethylhexyl)monoperoxycarbonate (Luperox TAEC) thermally decomposes into a t-amyloxy radical and a 2-ethylhexyloxycarboπate (2-EHOCO2) radical.
O O
Il Il
CH3CH2-C(CH3J2-OO-COCH2CH(C3H5)(C4H9) ^ f-amyloxy< + 2-EH-O-C-O - After the oxygen-oxygen bond cleavage, the t-amyloxy radical (102.3 Kcal/mol) can further decompose by β-scission to the ethyl radical (101.1 Kcal/mol) which is fast as ΔH= 1.2 Kcal/mol.
O
Il CH3CH2-C(CH3VO* (102.3 Kcal/mol) -» CH3CH2* (101.1 Kcal/mol) + CH3-C- CH3
The 2-ethyIhexyloxycarbonate (2-EHOCO2) radical can decarboxylate to a 2- ethylhexyloxy (2-EHO) radical which is fast as ΔH= 1.1 Kcal/mol.
C2H5 O C2H5
Luperox TBEC: OO-t-butyl-O-β-ethylhexyOmoπoperoxyearbonate ft-butylperoxy- 2-ethyIhexylcarbonate)
00-t-butyl-0-(2-ethylhexyl)monoperoxycarbonate (Luperox TBEC) thermally decomposes into
a t-butoxy radical and a 2-ethylhexyIoxycarbonate (2-EHOCO2) radical.
O O
Il I!
C(CH3)B-OO-COCH2CH(C2H5)(C4H9) ^ f-butoxy + 2-EH-O-C-O-
As described in the decomposition products of Luperox P, after the oxygen-oxygen bond cleavage, the t-butoxy radical (105.lK.cal/mol) can further decompose by β-scission to the methyl radical (104.9KcaI/mol) but this is a fairly slow or unlikely reaction as ΔH=0.2 Kcal/mol. O slow I'
C(CH3)3— O ' (105.1Kcal/mol) -> CH3 - (104.9Kcal/mol) + CH3-C-CH3
As described for Luperox TAEC, the 2-ethylhexyloxycarbonate (2-EHOCO2) radical can decarboxylate to a 2-ethyIhexyloxy (2-EHO) radical which is fast with ΔH= 1.1 Kcal/mol.
C2H5 O C2H5
CH-CH2-0-C-0 * (106 KcaJ/mol) -* CH-CH2-0 * (104.9 Kcal/mol) +
CO2 C4H9 C4Hg
Surprisingly, it was found that polymerization of a photochromic acrylic coating can be achieved with low yellow color. A basic photocliromic formulation is shown in Table 2.
Table 2
Weiεht f el cobalt naphthenate (a) 0,25 (phm) photochromic PC-A (b) 3 (phm) benzyl acrylate (c) 20
Ebeciyl 284N (d) 20
Ebecryl 1290 (e) 30
Ebecryl S411 (f) 30
Organic peroxide (g) 1.5 (phm)
(a) Sigma-Aldrich
(b) combination of photochromic materials (PC-A) to give a gray color upon UV exposure included: 45 weight percent of an indeno-fused naphthopyran that exhibited a blue color when irradiated with ultraviolet light (UV); 35 weight percent of an indeno- fused naphthopyran that exhibited a blue-green color when irradiated with UV; and 20 weight percent of an indeno-fused naphthopyran that exhibited a yellow-brown color when irradiated with UV. (c) Alfa-Aesar (d) (e), (f) Cytec (g) Arkema
The components in Table 2 are combined and mixed thoroughly to yield a photochromic coating.
A coated lens was made by the process in which a thermoplastic segmented lens substrate is first injection molded. The thermoplastic is polycarbonate. The mold block opens and photochromic coating from Table 2 is applied to the front surface of the segmented polycarbonate lens. The mold block then closes which serves two (2) purposes. First, when the mold block closes, it spreads the coating over the front convex (CX) surface of the segmented polycarbonate lens to provide a uniform thickness. Secondly, the mold block will provide suitable heat to cure the photochromic coating from Table 2. The mold block remains in contact with the coating for 1 -minute to produce a photochromic coated lens.
The photochromic lens was conditioned by exposure to UV to darken followed by a bleaching step in order to erase any exposure the photochromic may have seen previous to testing. Those skilled in the art are familiar with the conditioning of lenses for photochromic testing. One manner of conditioning lenses is described in U.S. Patent
7,320,826, column 42, lines 4 to 16. It should be understood that the intensity of the lights and the time of exposure may be varied to achieve conditioning of the lenses.
The photochromic lenses were measured for color using a Perkin-Elmer Lambda 900 to provide b* (yellow). Surprisingly, the photochromic coatings that were initiated using Luperox TAEC and Luperox TBEC have lower b* yellow of 4.7 and 2.9 respectively as reported in Table 3. The photochromic coating initiated using Luperox P shows a higher b* yellow of 6.8. A value of less than 5 is desired and more so a value less than 4 is prefered. Lupersol P differs from TAEC or TBEC in that it thermally decomposes to a benzoyloxy (BO) radical (106 Kcal/mol) which further decomposes to a high energy phenyl radical (113.1 Kcal/mol) which are thought to attribute to the high yellow color.
The possible radical species for each initiator are shown in Table 3 below, along with the b* yellow value corresponding to the photochromic coating.
Table 3: Free Radical Products Highest Energy
Organic Peroxide t-nmvioxy t-buloxy BO 2-EHOCO2 methyl ethyl 2-EIIO Phenyl b* yellow radicalfKcttl/m)
Luperox TAEC (b) x X x x 4.7 106 Luperox TBEC (a) x X x x 2.9 106 Luperox P (c) x x x X 6.8 113.1
(a) Arkema 00-t-butyl-0-(2-ethylhexyl)monoperoxycarbonate
(b) Arkema 00-t-amyl-0-(2-ethylhexyl)monoperoxycarbonate
(c) Arkema t-butylperoxybenzoate
The photochromic lens was measured on a Bench for Measuring Photochromies
(BMP) optical bench made by Essilor, France, in accordance with the procedure disclosed in U.S. Patent 7,320,826 at column 42, line 17 to column 43, line 30, except that the temperature dependence was not measured. The disclosure on the BMP testing is incorporated herein by reference. Color and optical density are measured while UV light activates the photochromic over a 15 minutes time period. The light is shut off, the photochromic bleaches and the color and optical density continue to be measured. We report the amount of light transmission after 15-minutes of UV exposure as %T dark 15 min. This tells us the relative darkening intensity. The rate at which darkening occurs is reported as TVi dark and the rate at which the photochromic bleaches is TYi fade. The T'/2 fade is the time interval in seconds for the ΔOD of the activated form of the photochromic compound in the test lens to reach one half the highest ΔOD after removal of the source of activating light. The T'Λ dark is the time interval in seconds of
irradiation that it takes to achieve 50% of the change in optical density (ΔOD) obtained after 15 minutes of irradiation.
Table 4 shows the photochromic performance T'Λ fade is significantly longer at 120 seconds using Luperox P.
Table 4
Organic Peoxide %T dark l5 min T Vi dark T '/z fade Luperox TBEC (a) 16 24 sec 99 sec Luperox TAEC (b) 13 23 sec 85 sec Luperox P (c) 14 29 sec 122 sec
(a) Arkema 00-t-butyl-0-(2-ethylhexyl)monoperoxycarbonate
(b) Arkema 00-t-amyI-0-(2-ethylhexyi)monoperoxycarbonate (c) Arkema t-butylperoxybenzoate
Another acrylic photochromic formulation is shown in Table 5, In this case, Akzo Triganox 131 t-amylperoxy-2-ethylhexyImonoperoxycarbonate (comparable to Luperox TAEC) was used
Table 5
Weight ( S) cobalt naphthenate (a) 0.25 photochromic PC-A (b) 3.0 organic peroxide (c) 1.5
SR423A (d) 1.0 benzyl acrylate (e) 19.0 SR399LV (f) 30 CN965 (g) 50
Optional additives*
Carbothane 3575A (h) 1.0 HALS (i) 1.0
(a) Sigma-AIdrich
(b) photochromic materials chosen to give a gray color upon UV exposure (PC-A) as described hereinbefore
(c) Akzo: Triganox 131 t-amylperoxy-2-ethylhexylcarbonate
(d) Sartomer isobornyl methacrylate
(e) Sans Ester
(f) Sartomer dipentaerythritolpentaacrylate (g) Sartomer aliphatic polyester urethane diacrylate
(h) Lubrizol Carbothane 3575 A (i) hindered amine light stabilizer
* Note those skilled in the art are familiar with the incorporation of additives. Such additives can be thermoplastic urethanes (TPU), hindered amine light stabilizers (HALS), antioxidants (AO), flow enhancing surfactants, leveling agents amongst others.
Table 6 shows Photochromic Coating Performance and includes b* at <4.0 using
Triganox 131 with or without the inclusion of Carbothane 3575A TPU. The TPU can be dissolved into monomers in an amount from 0.5 phm to 5,0 phm to increase viscosity or provide other useful properties, Akzo Triganox 131 is chemically the same as Arkema
Luperox TAEC.
Table 6
Example Car bo thane 3575A b^ 200hr SunTest 6a none 3.45 Pass
6b lphm 3.10 Pass
The SunTest is conducted by placing coated lenses into an Atlas Suntest CPS+ for 200 hours exposure and removed at predetermined intervals. Coating adhesion was tested by scoring the coating with a multi-razorblade device and then scoring again at 90 degrees. Tape was applied to the scored area and the tape was pulled. Adhesion passes if no coating is removed with the tape.
The above description provides general and specific guidelines for forming acrylate-based photochromic coating compositions. The compositions provide low yellowness coatings for thermoplastic lenses. They can be complemented with various dyes. A key component is the use of an organic peroxide having a free radical energy below 113 kcal/mol. For example, peroxyesters having free radical energy levels below 110 kcalΛnol, or in a range from about 100 to 106 kcal/mol may be used. It was discovered that free radicals with too high of an energy level can cause the radicals to interact with other components in the composition. The result of such interactions was observed as unacceptably high yellowness. The discovery is of particular value in protecting photochromic dye molecules from being attacked or damaged. The discovery is also applicable in protecting all dyes molecules from being attacked or damaged by free radical having too high of an energy level. The composition is well suited for use in a post-injection coating process, where the mold is used to spread the composition into a uniformly thin layer across the convex surface of the lens. This process uses the residual heat from the molten thermoplastic and the mold to cure the composition into a solid, abrasion resistant coaling. The in-mold process also allows the coating to achieve a high degree of conformity to the surface of bifocals, at the segment ridge, References to segmented lenses and multifocal lens means lenses having a ridge, which we also refer to as a lens surface discontinuity. These factors allow photochromic bifocal lens to be efficiently manufactured. Throughout the specification there are parenthetical references to (meth)acrylates. This notation refers to, and includes, the acrylate compound or the corresponding methacrylate version.
For all of the following examples, these thermally curable photochromic coating formulations were applied according to the post injection in-mold press coating process described above. It is preferred to obtain an optical article with high %T in the clear or non-colored state, good darkening, low yellow, fast fade back (bleaching) and low photochromic degradation (fatigue).
Table 7 shows various formulations using Cytec Ebecryl monomers. Various catalysts such as Trn-2-ethylhexanoate, King Industries K-Kat 348 bismuth carboxylate and Cobalt-naphthenate are used. Hostavin PR-31 HALS or a HALS - 1 is used with or without Ciba Irganox 1010 AO. Combinations of photochromic compounds that demonstrate a gray color (PC-A and PC-B) upon activation were used.
Attorney Docket: 139-29 (PCT)
Table 7 : Cvtec Ebecryl Formulations
O O
'Jl
Sn-2-EH: Tin-2-ethylhexanoate catalyst (Aldrich).
K-Kat 348: Bismuth carboxylatye catalyst (King Industries).
Co-N: cobalt naphthenate catalyst (Aldrich).
Hostavin PR-31: Propandioic acid, [4-methoxyphenyl)-methylene]-, bis-l,2,236.6-pentamethyl-4-piperidinyl) ester (Clarient).
HALS-I: phenyl-(3,5-di-tert.butyl-4-hydroxy-benzyl)-malonic acid-bis-(l,2J2,6J6-penta-methyl-4-piperidinyl)ester prepared as described
*o U.S. Patent 4,198,334 at column 14, line 59 to column 21, line 29, which disclosure is incorporated herein by reference.
Irganox 1010: Pentaerythritol Tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) hindered phenolic antioxidant (Ciba).
PC-A: previously described.
PC-B: Included: 5 weight percent of an indeno-fused naphthopyran that exhibited a blue-purple color when irradiated with ultraviolet light (UV); 10 weight percent of indeno-fused naphthopyrans that exhibited a blue color when irradiated with ultraviolet light (UV); 35 weight percent of a different indeno-fused naphthopyran that exhibited a blue color when irradiated with ultraviolet light (UV); 27 weight percent of an indeno-fused naphthopyran that exhibited a green-gray color when irradiated with ultraviolet light (UV); 23 weight percent of an indeno-fused naphthopyran that exhibited a green color when irradiated with ultraviolet light (UV).
SR506: isobornylacrylate (Sartomer).
HPMA: hydroxypropylmethacrylate (Aldrich).
284N: Ebecryl 284N aliphatic urethane diacrylate (Cytec) aliphatic urethane diacrylate diluted with a reactive diluent 1,6-hexanediol diacrylate. O
H
1290: Ebecryl 1290 hexafunctional aliphatic urethane acrylate (Cytec). w K*
8411: Ebecryl 8411 aliphatic urethane diacrylate (Cytec) aliphatic urethane diacrylate diluted with a reactive diluent isobomyl acrylate. O O
Triganox 131: tert-amylperoxy-2-ethylhexyl carbonate organic peroxide (Akzo).
00
O
Photochromic perfbπnance was measured using a BMP as previously described. Photochromic lenses are first conditioned (darkened then bleached) and initial transmission (Y) and color ( a*, b*) is measured. The photochromic is activated using a UV light source. After 15 minutes, the transmission is measured (%Tdark). The UV light source is shut off and a visible light source is turned on and the photochromic bleaches over a period of time. The amount of time it takes to reduce optical density by 50% is recorded (T'Λ). The transmission and color are continually monitored providing a darkening and fading rate and color diagram. Lenses are aged in a Weather-o-meter and the photochromic breakdown is monitored as %fatigue based on optical density loss and the change in yellow as Δb* in accordance with the procedure disclosed in U.S. Patent 6,998,072 at column 33, line 49 to column 34, line 11, which disclosure is incorporated herein by reference
Table 8 shows that formulas 1 - 5 preferred as they provide very good bleach transmission, low yellow color, good darkening, good fade kinetics and low photochromic fatigue <15%.
Table 8: Ebecryl Formulation Results, 60 sec, cure unless noted
Sample y b* %Tdark TVibleach %Fattøue Δb*
1 83.9 1.7 12.3 77 13.9 2.2
2 82.7 1.7 13.2 89 14.4 3.3 120 sec cure
3 81.5 1.6 14.8 60 10.8 3.7
4 80.0 1.5 15.5 61 5.6 3.0 120 sec cure
5 81.7 2.0 14.8 59 7.7 3.3
Table 9 shows various formulations using Sartomer monomers. Various catalysts such as Tin-2-ethylhexanoate, King Industries K-Kat 348 bismuth carboxylate and Cobalt-naphthenate are used. Hostavin PR-31 HALS or HALS-I is used with or without Ciba Irganox 1010 AO. Combinations of photochromic compounds that demonstrate a gray color (PC-A and PC-B) upon activation were used.
Table 9: Sartomer Formulations
Sn-2-EH; Tin-2-ethylhexanoate catalyst.
Co-N: cobalt naphthenate catalyst.
HALS-I: previously described.
Irganox 1010: Pentaerythritol TetrakisfS-fSjS-di-tert-butyl^- hydroxyphenyl)propionate) hindered phenolic antioxidant. PC-A: previously described.
SR506: Sartomer isobornylacrylate monomer.
BzA: Alpha Aesar Benzyl acrylate monomer.
HPMA: Aldrich hydroxypropylmethaciylate monomer.
SR-399: Sartomer dipenlaerythritol pentaacrylate monomer. CN-965: Sartomer aliphatic polyester based urethane diacrylate oligomer.
Trig 131: tert-Amylperoxy-2-ethyIhexyl carbonate organic peroxide.
Table 10 shows that formulas 7 and 8 are preferred as they provide very good bleach transmission, low yellow color, good darkening, good fade kinetics and low photochromic fatigue <15%.
Table 10: Sartomer Formulation Results, 60 sec cure
Sample Y b* %Tdark TKbleach %Fatiεue Ab*
6 79.6 4.1 13.9 JJ 10.7 4.1
7 81.2 1.7 13.2 48 6.1 3.7 8 80.8 1.7 13.7 49 5.8 4.1
The organic peroxide radicals are necessary to accelerate monomer curing.
However, the free radicals possess the potential to adversely interfere with other compounds within the coating. Antioxidants consume free radials. The formulations
according to the invention surprisingly provide a balance between providing protection from the free radicals without substantially effecting the radicals function in the monomer curing process.
The inclusion of Tin-2-ethylhexanoate (Sn-2-EH) as catalyst represents an improvement because it is provided in a colorless liquid. Some other metal catalysts require colored or oil-based solvents, winch can cause problems in optical applications. The Sn-2-EH resists coalescing and is able to dissolve in the coating monomers.
Furthermore, the formulations described herein are suitable for use in a post injection in-mold press coating process. To summarize, the coating formulations are based on the following combination of ingredients: Photochromic materials Antioxidant (AO) Metal salt catalyst - Initiator
Hindered amine light stabilizer
Monomers comprising at least one monofunctional (meth)acrylate and one multifunctional (meth)acrylate,
As can be seen from the test results, the various embodiments of the acrylate based coating formulations provide numerous benefits. The formulations provide excellent photochromic performance. In a preferred embodiment, the improved photochromic performance is combined with a segmented bifocal lens made from polycarbonate. The formulation can be utilized in a post-injection in mold press coat lens process. This represents an increase in efficiency over conventional coating methods. The formulation can be employed in an industrial molding and coating process as will discussed further below.
As can be seen in the flowchart of FIG. 1, the steps in the left column relates to formulating the coating composition. The primary components used to formulate the acrylate-based coating in step 10 will be discussed in greater detail below. The selection of suitable alkylperoxides based on dissociation energy in step 12 is discussed in greater detail above. The right column relates to steps performed by, or with, the injection molding machine. The process is commenced with the closing of
99
the mold, injecting resin in step 20 to provide a lens substrate, and optionally applying packing pressure. During this injection stage, a primary clamp force, of about 100 tons or more is utilized. Once the lens is rigid enough to sustain mold opening, the mold is opened, in step 22. Mold opening constitutes an upward vertical retraction of the movable side of the mold. This initial phase is conventional for injection molded lenses, for example, as described in U.S. Published Patent Application 2007/0138665, The substrate that could be used in this method could be any injection moldable lens material like PMMA, polycarbonate, polycarbonate/polyester blend, polyamide, polyurethane, polysulfone, cyclic olefin co-polymers, polystyrene, etc. In a preferred embodiment the substrate is polycarbonate.
The injecting step provides an afocal lens substrate, a single vision lens substrate, a multifocal lens, a bifocal lens substrate, a bifocal straight-top lens substrate, a trifocal lens substrate, a trifocal straight-top lens substrate, or a progressive lens substrate. In a preferred embodiment the lens is a segmented bifocal or trifocal lens.
One lens surface, for example the convex side, is exposed and facing upward. In step 24, the coating composition is applied to the exposed lens surface. The composition may be applied in step 24 a single, unpressurized charge, for example by a metering syringe mounted on a retractable arm that moves in between the open mold blocks. For lenses of all powers and configurations, the coating may be applied onto, or near, the center of the lens, off-center or at various locations. The lenses will all generally have a circular outer perimeter. One or more syringes may be employed to deposit coating composition, if the mold has 2, 4, or more lens molding cavities, After application of the composition and removal of the syringe, the movable mold half closes in step 26 to spread the coating across the entire upper lens surface. The coating is spread radially outwardly from the center, or near the center, of the lens, out to the circular periphery. During this cure stage, a secondary clamp force, less than or equal to the primary clamp force may be utilized. After the coating is cured, and the lens has solidified sufficiently, the mold is opened and the cured coated lens is ejected in step 28. The in-mold process is particularly well suited for coating a segmented bifocal lens. By re-clamping the mold to spread the coating, a uniformly thin layer is achieved and rapidly cured in situ. A high degree of mold replication assures that
coating does not build up at the surface discontinuity. Coating build-up is a long standing problem when attempting to add a photochromically enabled coating to a segmented, bifocal lens.
In a preferred embodiment, the photochromic materials are present in an amount of from 2.0 to 4.0 phm, and preferentially of 2.5 phm. The preferred Antioxidant is Irganox 101O3 and is present in an amount of 0.25 phm. The metal salt catalyst is either Sn-2-EH, Co-naphthenate or K-Kat348, and is present in an amount of 0.2 phm. The initiator is t-amylperoxy-2-ethyIlιexyl carbonate organic peroxide or t-butylperoxy-2-ethylhexylcarbonate. In a preferred embodiment, the initiator is Trig 131 (t-amylperoxy-2-ethylhexyl carbonate organic peroxide, present in an amount of 1.5 phm. The HALS is phenyl-(3,5-di-tert.butyl-4-hydroxy-benzyl)-malonic acid-bis- (l,2J2,6J6-penta-methyl-4-piperidinyl)ester or Hostavin PR-31. The preferred HALS is phenyl-(355-di-tert,butyl-4-hydroxy-benzyl)-malonic acid-bis-(l ,2,2,6,6-penta- mediyl-4-piperidinyl)ester present in an amount of 1 phm. The monomer blend comprises a mixture of at least two different monofunctional (meth)acrylate monomer and/or difunctional meth(acrylate) monomer selected from isobornylacrylate monomer (SR506), 2-hydroxypropylmethacrylate monomer (HPMA), benzyl acrylate monomer (BzA)1 polyethyleneglycol (600) dimethacrylate (SR252), ethoxylaled (8) bisphenol A dimethacrylate (CD542), ethoxylated (10) bisphenyl A diacrylate (SR602), and ethoxylated (30) bisphenyl A dimethacrylate (SR9036), polyethyleneglycol (400) diacrylate (SR344), polyethyleneglycol (400) dimethacrylate (SR603), polyethyleneglycol (600) diacrylate (SR610), ethoxylated (4) bisphenol A diacrylate (SR601), ethoxylated (4) bisphenol A dimethacrylate (SR540), ethoxylated (6) bisphenol A dimethacrylate (SR541), ethoxylated (10) bisphenyl A dimethacrylate (SR480), ethoxylated (30) bisphenyl A diacrylate (CD9038). The monomers from this category are present in an amount of 15% by weight.
Additionally, the monomer blend includes one multifunctional (meth)acrylate monomer selected from hexafunctional aliphatic urethane acrylate (Ebecryl 1290) and dipentaerythritol pentaacrylate monomer (SR399), (present in an amount of 33% by weight) and at least one aliphatic urethane diacrylate selected from Ebecryl 284N,
Ebecryl 8411, and CN965 (present hi an amount of 52% by weight).
The catalyst is a metal ester chosen from a large range of organic acid esters including alkane esters such as acetates, heptanoates, hexanoates, octoates, decanoates, oleates, stearates, oxalates, salicylates, linoleates and lactates. Aromatic esters such as naphthenates. Other non-limiting examples of suitable metal esters include bismuth naphthenate, calcium naphthenate, calcium octoate, cerium octoate, chromium octoate, cobalt octoate, copper naphthenate, copper octoate, ferric octoate, lead naphthenate, lead octoate, lithium neodecanoate, manganese naphthenate, manganese octoate, molybdenum naphthenate, molybdenum octoate, nickel octoate, potassium octoate, sodium naphthenate, sodium octoate, strontium octoate, vanadium naphthenate, vanadium octoate, Yttrium octoate, zinc naphthenate, zinc octoate and zirconium octoate. Metal salts are also known as soaps.
A preferred metal salt is Tin octoate (2-ethylhexanoate) which comes as a pure liquid with light straw yellow color and devoid of solvent, which makes it desirable for demanding optical coating applications. Another family organotins (tin-carbon bonds) used as catalysts are hydrated monobutyltin oxides which can include butyl chlorotin dihydroxide, butyltin tris (2-ethylhexoate), dibutyltin diacetate, dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin distearate, butyl stannoic acid, dioctyltin dilaurate and dioctyltin maleate, inter alia. A preferred metal salt is tin-2-ethylhexanoate, bismuth carboxylate, or cobalt naphthenate.
Antioxidants (AO) which are suitable for use in the coating according to the invention are described below. The preferred antioxidant is Irganox 1010.
Irganox 1010: Pentaerythritol Tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate) Family: sterically hindered phenolic 100%, white powder IRGANOX 1010
Irganox 1098: diamide derivative, N.N'-hexane-ljό-didiylbis^jS-di-tert-butyl-^- hydroxyphenylpropionamide)) Family: sterically hindered phenolic 100%, white powder
IRGANOX 1Q9B
Irganox 245: Ethylenebis(oxyetIiylene)bis-(3-(5-tert-butyl-4-4hydroxy-m-tolyl)- propionate) Family: sterically hindered phenolic 50%-100%, white powder
IRGANOX 245
The HALS (Hindered Amine Light Stabilizer) which are suitable for use in the coating formulations possess hindered phenolic antioxidant properties. The preferred HALS is phenyI-(3,5-di-tert.butyI-4-hydroxy-benzyl)-malonic acid-bis-(l, 2,2,6,6- penta-methyl-4-piperidinyl)ester. These compounds are described more fully in U.S. Patent 4,198,334. Surprisingly, it was discovered that the (a) choice of photochromic material and concentration, (b) in combination with the choice of Hals and (c) in further combination with the choice of the monomer system (Ebecryl) is very important to improve the photochromic level and properties of the lens in term of %T dark, %T bleach, photochromic fatigue and yellow residual color.
The photochromic materials can include the following classes of photochromic compounds: chromenes, e.g., naphthopyrans, benzopyrans, indenonaphthopyrans, phenanthropyrans or mixtures thereof; spiropyrans, e.g., spiro(benzindoline)naphthopyrans, spiro(indoLine)benzopyrans, spiro(indoline)naphtbopyrans, spiro(indoline)quinopyrans and spiro(indoHne)pyrans; oxazines, e.g., spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzuidoline)naphthoxazines and spiro(indoline)benzoxazines; fulgides, fulgimides and mixtures of such photochromic compounds.
Non-limiting examples of chromenes are described in U.S. Patents 5,458,814 at column 2, line 18 to column 9, line 5; 5,645,767 at column 2, line 16 to column 11, line 67; 5,656,206 at column 2, line 5 to column 13, line 50; 5,658,501 at column 2,
Iine S to column 11, line 31; 5,698,141 at col. 2, line 11 to col. 19, line 19; 5,723,072 at column 2, line 27 to column 15, line 4; 6,022,497 at col. 2, line 21 to col. 10, line
60; 6,113,814 at column 2, line 23 to column 23, line 29; 6,153,126 at column 2, line 26 to column 8, line 8; 6,296,785 at column 2, line 55 to column 30, line 27;
6,340,766 at column 3, line 12 to column 13, line 19; 6,348,604 at column 3, line 35 to column 16, line 37; 6,353,102 at column 2, line 3 to column 11, line 7; 6,555,028 at column 2, line 40 to column 24, line 55; 7,342,112 at column 2, line 38 to column
78, line 13; 7,465,415 at column 8, line 58 to column 74, line 64; 7,527,754 at column 2, line 65 to column 16, line 10; U.S. Patent Publication 2006/0228557 at paragraph
[0007] to [0115]; ; U.S. Patent Publication 2007/0138449 at paragraph [0010] to
[0101]; and U.S. Patent Publication 2008/0103301 at paragraph [0007] to [0115]. The
disclosures of the aforementioned patents on chromene photochromic materials are incorporated herein by reference.
Non-limiting examples of spiropyrans are described in U.S. Patents 4,931,220 at column 11, line 66 to column 13, line 20; U.S. Patent 5,236,958 at column 1, line 43 to column 7, line 43; and 5,252,742 at column 1, line 45 to column 6, line 60. The disclosures of the aforementioned patents on spiropyrans are incorporated herein by reference, Spiro(indoline)pyrans are also described in the text, Techniques in Chemistry, Volume III, "Photochromism", Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971.
Non-limiting examples of oxazines are described in U.S. Patents 4,637,698 at column 1, line 40 to column 2, line 23; 4,931,219 at column 1, line 45 to column 7, line 9; 5,166,345 at column 3, line 36 to column 7, line 42; and 5,821,287 at column 3, lines 7 to 51. The disclosures of the aforementioned patents on oxazines are incorporated herein by reference.
Non-limiting examples of fulgides and fulgimides are disclosed in U.S.
Patents 4,685,783 at column 1, line 57 to column 5, line 27; 4,931,220 at column 21, line 39 to column 22, line 40; and 5,359,085 at column 5, line 26 to column 19, line 45. The disclosures of the aforementioned patents on fulgides and fulgimides are incorporated herein by reference.
The photochromic materials described herein can be chosen from a variety of non-limiting examples which include: of course, a single photochromic compound; a mixture of photochromic compounds; a material comprising at least one photochromic compound, such as a plastic polymeric resin or an organic monomelic or oligomeric solution; a material such as a monomer or polymer to which at least one photochromic compound is chemically bonded; a material comprising and/or having chemically bonded to it at least one photochromic compound, the outer surface of the material being encapsulated (encapsulation is a form of coating), for example with a polymeric resin or a protective coating such as a metal oxide that prevents contact of the photochromic material with external materials such as oxygen, moisture and/or chemicals that have a negative effect on the photochromic material, such materials can be formed into a particulate prior to applying the protective coating as described
in U.S. Patents 4,166,043 and 4,367,170; a photochromic polymer, e.g., a photochromic polymer comprising photo chromic compounds bonded together; or mixtures thereof.
The above description provides general guidelines and specific formulations for acrylate-based photochromic coating compositions. The compositions result in coatings having low yellowness and high photochromic performance for thermoplastic lenses. The composition is well suited for use in a post-injection in- mold press coating process, where the mold is used to spread the composition into a uniformly thin layer across the convex surface of the lens, This process uses the residual heat from the molten thermoplastic and the mold to cure die composition into a solid, abrasion resistant coating. The in-mold process also allows the coating to achieve a high degree of conformity to the surface of bifocals, at the segment ridge. References to segmented lenses and multifocal lens means lenses having a ridge, which we also refer to as a lens surface discontinuity. These segmented lenses are also referred to as straight-top bifocal lenses. These factors allow photochromic bifocal lens to be efficiently manufactured. Throughout the specification there are parenthetical references to (meth)acrylates. Tins notation refers to, and includes, the acrylate compound or the corresponding methacrylate version.
Having described preferred embodiments for lens manufacturing, materials used therein and methods for processing the same (which are intended to be illustrative and not limiting), it is noted that modifications and variations can be made by persons skilled in the art in light of the above teachings. It is therefore understood that changes may be made in the particular embodiments of the invention disclosed which are within the scope and spirit of the invention as outlined by the appended claims. Having thus described the invention with the details and particularity required by the patent laws, what is claimed and desired protected by Letters Patent is set forth in the appended claims.
Claims
1. A thermally curable photo chromic coating composition comprising: a mixture having two different monomers, where the monomers are selected from the group consisting of: (a) monofunctional (meth)acrylate; (b) difunctional (meth)acrylate; (c) a combination of a monofunctional (meth)acrylate and a difunctional (meth)acrylate; (d) multifunctional (meth)acrylate; and (e) aliphatic urethane diacrylate; a metal salt catalyst; a Hindered Amine Light Stabilizer (HALS); an antioxidant; an initiator; and a photochromic dye.
2. A method for manufacturing an injection molded thermoplastic photochromic bifocal lens comprising the steps of: providing an acrylate-based photochromic coating composition including two different types of monomers, a metal salt catalyst, a Hindered Amine Light Stabilizer
(HALS), an antioxidant, an initiator and a photochromic dye; injecting molten thermoplastic into an edge-gated bifocal-lens forming cavity of an injection molding machine having a vertical equipment axis to provide a bifocal lens substrate; opening the mold at a time when the bifocal lens is rigid enough to retain its shape; applying the photochromic composition onto the bifocal lens substrate; and
closing the mold to spread the photochromic composition into a uniformly thin layer so that residual heat from the molding machine cures the photochromic composition into a coating with low photochromic fatigue and reduced yellowing.
3. A method according to claim 2, wherein the monomers are selected from the group consisting of: (a) monofunctional (meth)acrylate; (b) difunctional (meth)acrylate; (c) a combination of a monofunctional (meth)acrylate and a difunctional (meth)acrylate; (d) multifunctional {meth)acrylate; and (e) aliphatic urethane diacrylate.
4. A method according to claims 2 or 3, wherein the photochromic coating is applied across a segmented surface of the bifocal lens to a thickness in the range from about 1 to 10 μm, and wherein the photocliromic fatigue is less than 15% and the %T dark is less man 16%.
5. A composition according to claim 1 or a method according to claims 2, 3 or 4, wherein the metal salt is selected from the group consisting of a metal ester of 2- naphthoic acid, a metal ester of 2-ethylhexanoic acid, a metal ester of octoate material, and combinations thereof, preferably tin-2-ethylhexanoate, bismuth carboxylate, cobalt naphthenate and combinations thereof.
6. A composition according to claims 1 or 5 or a method according to any of claims 2 to 5, wherein the HALS is selected from the group consisting of [4-(methoxyphenyl)~ methylene]-bis-l,2J2,636-pentamethyl-4-piperidinyl-propanedioic acid ester and phenyl-(3,5-di-tert.butyl-4-hydroxy-benzyl)-malonic acid-bis-(l,2,2,6,6-penta- methyl-4-piperidinyl)ester and preferentially phenyl-(3,5-di-tert.butyl-4-hydroxy- benzyl)-malonic acid-bis-(l,2,2,6,6-penta-methyl-4-piperidinyl)ester .
7. A composition according to claims 1, 5 or 6 or a method according to any of claims 2 to 6, wherein the antioxidant is a sterically hindered phenolic compound and preferably a pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate]hindered phenolic compound.
8. A composition according to any of claims 1 or 4 to 7 or a method according to any of claims 2 to 7, wherein the initiator comprises an organic peroxide which presents a free radical energy less than about 113 kcal/mol at 298 K, preferably t-amylperαxy-2- ethylhexyl carbonate organic peroxide or t-butylperoxy-2-ethylhexylcarbonate.
9. A composition according to any of claims 1 or 4 to 8 or a method according to any of claims 2 to 8, wherein the monofunctional (meth)acrylate is selected from the group consisting of isobornylacrylate, hydroxypropyhnethacrylate, benzyl acrylate and combinations thereof.
10. A composition according to any of claims 1 or 4 to 9 or a method according to any of claims 2 to 9 wherein the difunctional (meth) acrylate is selected from the group consisting of polyethyleneglycol (600) dimethacrylate, ethoxylated (8) bisphenol A dimetbacrylate, ethoxylated (10) bisphenyl A diacrylate , and ethoxylated (30) bisphenyl A dimethacrylate.
I L A composition according to any of claims 1 or 4 to 10 or a method according to any of claims 2 to 10 wherein the multifunctional (meth)acrylate is selected from the group consisting of hexafunctional aliphatic urethane acrylate and dipentaerythritol pentaacrylate.
12. A composition according to any of claims 1 or 4 to 11 or a method according to any of claims 2 to 11, wherein the aliphatic urethane diacrylate is selected from the group consisting of aliphatic polyester urethane diacrylate, aliphatic urethane diacrylate diluted with a reactive diluent 1,6-hexanediol diacrylate, aliphatic urethane diacrylate diluted with a reactive diluent isobornyl acrylate and combinations thereof.
13. A composition according to any of claims 1 or 4 to 12 or a method according to any of claims 2 to 12, wherein: the monomers of (a) monofunctional (meth)acrylate; (b) difunctional
(meth)acrylate; and (c) a combination of a monofunctional {meth) acrylate and a difunctional (meth)acrylate are present in an amount from 10% to 25% by weight; the monomers of (d) multifunctional (meth) acrylate are present in an amount from 20% to 40% by weight; the monomers of (e) aliphatic urethane diacrylate are present in an amount from 50% to 70% by weight; the metal salt is present in an amount from 0.10 phm to 0,30 phm; the Hindered amine light stabilizer (HALS) is present in an amount from 1.00 phm to 5.00 phm; the antioxidant is present in an amount from 0.20 phm to 0.50 phm; the initiator is present in an amount from 1.00 phm to 2.00 phm; and the photochromic dye is presents in an amount from 1.00 phm to 5.00 phm.
14. A composition according to any of claims 1 or 4 to 13 or a method according to any of claims 2 to 13, wherein the monomer of (a) monofunctional (meth) acrylate
comprises a mixture of isobornyl acrylate in an amount from 1% to 5% by weight and benzyl acrylate or 2-hydroxypropylmethacrylate in an amount from 10% to 21%.
15. A composition according to any of claims 1 or 4 to 14 or a method according to any of claims 2 to 14, wherein the mixture of monomers comprises isobornylacrylate present in an amount of 5% by weight, hydroxypropyhneύiacrylate present in an amount of 10% by weight, aliphatic urethane diacrylate preferably Ebecryl 8411 present in an amount of 18% by weight, hexafunctional aliphatic urethane acrylate preferably Ebecryl 1290 present in an amount of 33% by weight, and aliphatic urethane diacrylate preferably Ebecryl 8411 present in an amount of 34% by weight; the metal salt comprises tin-2-ethylheχanoate present in an amount of 0.14 phm; the Hindered amine light stabilizer (HALS) comprises bis (1,2,2,6,6- pentamethyI-4-piperidinyl)-[[3 ,5-bis-(l , l-dimethylethyl)-4- hydroxyphenyl]methyl]butylmalonate or phenyl-(3,5-di-tert.butyl-4-hydroxy-benzyl)- malonic acid-bis-(ls2,2,6,6-penta-methyl-4-piperidinyl)ester preferably phenyl-(3,5- di-tert.butyI-4-hydroxy-benzyl)-malonic acid-bis-( 1 ,2,2,6,6-penta-methyl-4- piperidinyl)ester present in an amount of 1 phm; the antioxidant comprises pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate] hindered phenolic compound preferably Irganox 1010 present in an amount of 0.25 phm; the initiator comprises t-amyIperoxy-2-ethylhexyl carbonate organic peroxide preferably Triganox 131 present in an amount of 1.5 phm; and the photochromic dye is present in an amount of 2.0 to 4.0 phm, preferably
2.5 phm.
16. A composition according to any of claims 1 or 4 to 15 or a method according to any of claims 2 to 15, further comprising a thermoplastic polyurethane (TPU), preferably present in an amount from 0.5 phm to 5,0 phm.
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US12/999,080 US8512604B2 (en) | 2008-06-19 | 2009-06-18 | Photochromic coating exhibiting improved performance and reduced yellowness |
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US12/142,452 | 2008-06-19 | ||
US12/142,452 US8048974B2 (en) | 2008-06-19 | 2008-06-19 | Initiators for optical coating formulations with reduced yellowness |
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WO2018182821A1 (en) | 2017-03-28 | 2018-10-04 | Ford Global Technologies, Llc | Stabilized additive manufacturing articles |
BR112021010078A2 (en) * | 2020-02-28 | 2022-09-20 | Jiangsu Conant Optical Co Ltd | PHOTOCHROMIC RESIN LENS WITH A REFRACTIVENESS OF 1.50 AND METHOD FOR PREPARING A PHOTOCHROMIC RESIN LENS WITH A REFRACTIVENESS OF 1.50 |
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US20090318619A1 (en) | 2009-12-24 |
US20110115108A1 (en) | 2011-05-19 |
US8512604B2 (en) | 2013-08-20 |
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