EP0195898B1 - A method of increasing the light fatigue resistance of a photochromic composition and photochromic composition - Google Patents
A method of increasing the light fatigue resistance of a photochromic composition and photochromic composition Download PDFInfo
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- EP0195898B1 EP0195898B1 EP86101289A EP86101289A EP0195898B1 EP 0195898 B1 EP0195898 B1 EP 0195898B1 EP 86101289 A EP86101289 A EP 86101289A EP 86101289 A EP86101289 A EP 86101289A EP 0195898 B1 EP0195898 B1 EP 0195898B1
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- European Patent Office
- Prior art keywords
- carbon atoms
- alkyl
- hydrogen
- photochromic
- hindered amine
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 34
- 239000004611 light stabiliser Substances 0.000 claims abstract description 33
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims abstract description 13
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003003 spiro group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- -1 Ni2+ ion Chemical class 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 5
- LXRZJOUAIRAIPX-UHFFFAOYSA-N 3-[1-(3,5-ditert-butyl-4-hydroxyphenyl)-5,5-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)pentoxy]-3-oxopropanoic acid Chemical compound C1C(C)(C)N(C)C(C)(C)CC1C(C1CC(C)(C)N(C)C(C)(C)C1)CCCC(OC(=O)CC(O)=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 LXRZJOUAIRAIPX-UHFFFAOYSA-N 0.000 claims description 3
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 claims description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 3
- ZVRLGOKQDHVWSZ-UHFFFAOYSA-L cobalt(2+);n,n-di(propan-2-yl)carbamodithioate Chemical compound [Co+2].CC(C)N(C(C)C)C([S-])=S.CC(C)N(C(C)C)C([S-])=S ZVRLGOKQDHVWSZ-UHFFFAOYSA-L 0.000 claims description 3
- JIJSLRQORTUOBN-UHFFFAOYSA-L nickel(2+);oxido-propan-2-yloxy-propan-2-ylsulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound [Ni+2].CC(C)OP([O-])(=S)SC(C)C.CC(C)OP([O-])(=S)SC(C)C JIJSLRQORTUOBN-UHFFFAOYSA-L 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 claims description 3
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 claims description 2
- PGHVFXYMFJCNJE-UHFFFAOYSA-K cobalt(3+) N,N-dibutylcarbamodithioate Chemical compound C(CCC)N(C([S-])=S)CCCC.[Co+3].C(CCC)N(C([S-])=S)CCCC.C(CCC)N(C([S-])=S)CCCC PGHVFXYMFJCNJE-UHFFFAOYSA-K 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 2
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229940116351 sebacate Drugs 0.000 claims 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000005281 excited state Effects 0.000 abstract description 9
- 239000000975 dye Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 14
- 239000012963 UV stabilizer Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 0 CC1CC(*)(*)N(C)C(C)(*)C1 Chemical compound CC1CC(*)(*)N(C)C(C)(*)C1 0.000 description 5
- 239000013068 control sample Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 4
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000012965 benzophenone Substances 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
- 238000005266 casting Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WPRMJBJYCFNTKE-UHFFFAOYSA-L (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinate;nickel(2+) Chemical compound [Ni+2].CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WPRMJBJYCFNTKE-UHFFFAOYSA-L 0.000 description 1
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical class CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- IVVLFHBYPHTMJU-UHFFFAOYSA-N 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11^{8}.2^{6}]henicosan-21-one Chemical compound C1C(C)(C)NC(C)(C)CC21C(=O)NC1(CCCCCCCCCCC1)O2 IVVLFHBYPHTMJU-UHFFFAOYSA-N 0.000 description 1
- JHQVCQDWGSXTFE-UHFFFAOYSA-N 2-(2-prop-2-enoxycarbonyloxyethoxy)ethyl prop-2-enyl carbonate Chemical compound C=CCOC(=O)OCCOCCOC(=O)OCC=C JHQVCQDWGSXTFE-UHFFFAOYSA-N 0.000 description 1
- MHCGTEBQHSVRDP-UHFFFAOYSA-N 3-(3',3'-dimethyl-6-nitrospiro[chromene-2,2'-indole]-1'-yl)propanoic acid Chemical class O1C2=CC=C([N+]([O-])=O)C=C2C=CC21N(CCC(O)=O)C1=CC=CC=C1C2(C)C MHCGTEBQHSVRDP-UHFFFAOYSA-N 0.000 description 1
- AOKSGDQCBLFYPP-UHFFFAOYSA-N CC(CC(C1N)(N)NC)(CC1(N)O)O Chemical compound CC(CC(C1N)(N)NC)(CC1(N)O)O AOKSGDQCBLFYPP-UHFFFAOYSA-N 0.000 description 1
- BOCUEGPAFFXFEK-UHFFFAOYSA-N CCCNC(C)=C Chemical compound CCCNC(C)=C BOCUEGPAFFXFEK-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- BAGDYXSZQVQPKH-UHFFFAOYSA-M [Ni+].CC(C)OP([O-])(=S)SC(C)C Chemical compound [Ni+].CC(C)OP([O-])(=S)SC(C)C BAGDYXSZQVQPKH-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 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
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- HPOWMHUJHHIQGP-UHFFFAOYSA-L n,n-dibutylcarbamodithioate;nickel(2+) Chemical compound [Ni+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC HPOWMHUJHHIQGP-UHFFFAOYSA-L 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
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- IAHPADQGUAKOQZ-UHFFFAOYSA-N spiro[1,3-dihydroindole-2,3'-benzo[f][1,4]benzoxazine] Chemical compound C1=CC=CC2=C(N=CC3(NC4=CC=CC=C4C3)O3)C3=CC=C21 IAHPADQGUAKOQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
Definitions
- the invention relates to a method of increasing the light fatigue resistance of a photochromic composition and a photochromic composition.
- This invention relates more particularly to an organic photochromic composition comprising spiro lindoline-2,3'-[3LH]-napht[2,1-N[lA]oxazine] (S.O.) dye and unconventional ultraviolet (UV) stabilizers.
- photochromic compounds Compounds which undergo reversible photo-induced color changes are termed photochromic compounds. When subjected to ultraviolet light or visible irradiation, these photochromic compounds change their transmission. They subsequently revert to their original color state when they are subjected to a different wavelength of radiation or when the initial light source is removed.
- organic photochromic materials have been known for over 50 years, they have not had widespread industrial or commercial use. This is primarily due to the irreversible decomposition phenomenon, generally known as light fatigue. Repeated exposure to light causes the photochromic materials to lose their photochromism.
- U.S. Patent No. 3 212 898 teaches the use of conventional UV absorbers such as benzophenone and benzotriazole to increase the photochromic life of photochromic benzospiropyran compounds.
- U.S. Patent No. 3 666 352 teaches the use of conventional UV light absorbers in photochromic mercury thiocarbazonate lenses, transparent to radiation of wavelengths greater than 420 nm and opaque to radiation of wavelengths less than 420 nm in order to substantially increase the durability of the lenses against photochemical degradation.
- One class of organic photochromic compounds spiro[indoline-2,3'-[3N-naphth[2,1-bl[1,4]oxazine] dyes (S.O. dyes) are known to have good light fatigue resistance. In general, the light fatigue resistance of the spirooxazine compounds is about 100 times better than the closely related spiropyrans.
- This class of photochromic compounds has been disclosed in U.S. Patent Nos. 3 562 172; 3 578 602; 4 215 010; 4 342 668; and 4440672.
- Acids may be in the plastic host material from which the photochromic article is made, such as PVC or cellulosics.
- the acids are usually generated either thermally during the forming process, or photochemically during use of the photochromic article.
- the S.O. dye solution becomes a pinkish to reddish color in the presence of even a minute amount of acid, and the solution ceases to show a photochromic effect.
- the pinkish to reddish color is likely due to the formation of a complex between the S.O. compound and acid.
- a base must be used to neutralize the acid and to restore the original colorless or light blue color.
- U.S. Patent No. 4 440 672 discloses the use of organonickel complex stabilizers to improve the light fatigue resistance of the photochromic compounds. However, these organonickel complexes do not have the ability to neutralize acids which may be present.
- the problems of the prior art are overcome by the discovery that a group of unconventional UV stabilizers will improve the light-fatigue resistance of S.O. dyes, while not affecting their photocolorability.
- These unconventional UV stabilizers belong to the class of hindered amine light stabilizers (HALS) and excited state quenchers.
- Hindered amine light stabilizers offer an advantage over organometallic complex stabilizers in their ability to neutralize acid, and to thus improve the light-fatigue resistance and preserve the original color of the S.O. dyes. It is preferable to use the hindered amine light stabilizers together with excited state quenchers in the organic photochromic compound of the invention; this combination has a synergetic effect in improving the light fatigue resistance of the S.O. compounds.
- UV stabilizers will not hinder the photocolorability of S.O. dyes, since they have a minimal absorption in the UV region where S.O. dyes absorb.
- the S.O. dye and UV stabilizers may be incorporated within optically clear plastics to make a photochromic element suitable for a photochromic sunglass lens, ski goggle, or other plastics to render them photochromic.
- the present invention improves the light fatigue resistance of an organic photochromic composition containing S.O. dye.
- the present invention further improves the light fatigue resistance of these photochromic compositions without hindering their photocolorability.
- the present invention allows to use such improved photochromic compositions to fabricate photochromic articles such as sunglasses, ophtalmic lenses, ski goggles, window coatings, toys, fabrics, and the like.
- the organic photochromic composition of the present invention comprises: a) spiro [indoline-2,3'-[3H]-naphth[2,1-b][1,4]oxazine] dye (spirooxazine dye), having the structural formula wherein one of R 1 , R 2 and R 3 is hydrogen, halogen, lower alkyl, or lower alkoxy and the others are hydrogen; R 4 and R 5 are hydrogen lower alkyl, lower alkoxy, halogen, or trifluoromethyl; and R 6 is lower alkyl; and, b) an unconventional UV stabilizer or stabilizers.
- the UV stabilizer comprises a hindered amine light stabilizer (HALS).
- HALS hindered amine light stabilizer
- the preferred hindered amine light stabilizers comprise derivatives of tetramethyl piperidine.
- the UV stabilizer comprises a combination of a hindered amine light stabilizer and an excited state quencher.
- the excited state quencher comprises an organonickel complex light stabilizer.
- the S.O. dye and UV stabilizers may be mixed in a solution with an optically clear polymer which is thereafter cast as a film, sheet, lens, or toy, or a polymer which is injection molded or otherwise shaped into a film or lens; or a prepolymerized film or lens containing the UV stabilizers may he immersed in a dye bath comprising S.O. dye dissolved in a solution of organic solvents such as alcohol, toluene, halogenated hydrocarbon or the like.
- Other methods of blending the UV stabilizers with the S.O. dye and polymers, such as coating or laminating may also be employed.
- Another hindered amine iight stabilizer which is useful in the organic photochromic composition of the invention comprises the structural formula wherein R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are lower alkyl; and R 3 and R 8 are lower alkyl or hydrogen; and in particular, the hindered amine light stabilizer is di(1,2,2,6,6-pentamethyl-4-piperidinyl)-butyl(3',5'-ditertbutyl-4-hydroxybenzyl) malonate, wherein R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , Rg, R 10 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are methyl, R 11 is butyl, and R 3 and R 8 are methyl, sold under the tradename of
- Ultraviolet stabilizers belonging to the class of excited state quenchers, which are useful in the organic photochromic compound of the invention, include complexes of Ni 2 + ion with some organic ligand, cobalt (III) tris-di-n-butyldithiocarbamate, cobalt (II) diisopropyldithiocarbamate (Co DIPDTP), and nickel diisopropyldithiophosphate (Ni DIPDTP).
- the preferred excited state quenchers are singlet oxygen quenchers, and in particular, complexes of Ni 2+ ion with some organic ligand. These Ni 2+ complexes are normally used in polyolefins to provide protection from photodegradation. Most preferably, the Ni 2+ complexes are: [2,2'-Thiobis [4-(1,1,3,3-tetramethylbutyl) phenolato] (butylamine)] nickel, having the structural formula sold under the tradename of Cyasorb UV 1084, and obtained from the American Cyanamid Company;
- Nickel [0-ethyl (3,5-di-tert-butyl-4-hydroxybenzyl)] phosphonate having the structural formula sold under the tradename of Irgastab 2002, and obtained from the Ciba-Geigy Corporation
- Nickel dibutyldithiocarbamate having the structural formula sold under the tradename of Rylex NBC, and obtained from E.I. duPont de Nemours & Company
- Rylex NBC e.I. duPont de Nemours & Company
- S.O. dyes for use in accordance with the invention are 1,3,3,4,5-pentamethyl-9'-methoxy-spiro [indoline-2,3'-[3H]-naphth [2,1-b] [1,4] oxazine;
- the preferred plastic hosts are cellulose acetate butyrate (CAB); CR-39 TM , a diethylene glycol bis (allyl carbonate) obtained from PPG Industries, Inc.; Lexan TM , a polycarbonate resin condensation product of bisphenol-A and phosgene, obtained from General Electric; Plèxiglas TM , a polymethyl methacrylate obtained from the Rohm and Haas Company; polyvinyl chloride; and polyolefins.
- CAB cellulose acetate butyrate
- CR-39 TM a diethylene glycol bis (allyl carbonate) obtained from PPG Industries, Inc.
- Lexan TM a polycarbonate resin condensation product of bisphenol-A and phosgene, obtained from General Electric
- Plèxiglas TM a polymethyl methacrylate obtained from the Rohm and Haas Company
- polyvinyl chloride polyolefins.
- CAB samples having a thickness of 0,43 - 0,48 mm (17 - 19 mls), containing 0.4 % by weight of a mixture of 1,2,3,3,4,5- and 1,2,3,3,5,6-hexamethyl-9'-methoxy S.O. isomers, with and without hindered amine light stabilizers (HALS) were prepared by casting a methylene chloride solution of CAB. Four successive castings were needed to obtain the desired thickness with good optical appearance.
- the control sample contained no HALS.
- the seven other samples contained various hindered amine light stabilizers in an arbitrary amount of 0.4 % by weight. The samples were subjected to a 20-hour cycle Fadeometer exposure testing.
- CAB sheet samples (1,52 mm/60 mls) ware made by injection molding.
- One of the CAB sheet samples had 0.2 % by weight of a mixture of 1,2,3,3,4,5- and 1,2,3,3,5,6-hexamethy)-9'-methoxy spirooxazine isomers and 0.2 % by weight of UV-Chek AM-205 as an excited state quencher.
- the other sample also had 0.2 % by weight Tinuvin 622 as a hindered amine light stabilizer in addition to the S.O. dye and the UV-Chek AM-205.
- the sample without the HALS lost all of its photochromism after 15 20-hour Fadeometer exposure cycles. However, the sample with the HALS still had 40 % of the original photocolorability left.
- a control sample was cast at 160° in an oven for 20 minutes from a plastisol solution consisting of 31 % diisodecylphthalate, 3 % octyl epoxy tallate, 3 % mark stabilizer, 63 % PVC and 0.1 % 1,3,3,4,5- and 1,3,3,5,6-pentamethyl-9'-methoxy S.O. dye mixture.
- Two more samples were prepared as follows: One sample had, in addition to the ingredients in the control sample, 0.2 % by weight UV-Chek AM-205, and the other sample had 0.2 % by weight UV-Chek AM-205 and 1.0 % by weight Tinuvin 622.
- the control sample lost all of its photochromic effect after 20 hours of Fadeometer exposure; the sample with UV-Chek AM-205 lasted 80 hours before losing its photochromic effect, and the sample with both UV-Chek AM-205 and Tinuvin 622 lasted 180 hours before losing its photochromic effect.
- An ethanol solution of 1,3,3-trimethyl S.O. dye was prepared by dissolving 13.1 mg of dye in 100.0 ml of ethanol. Two milliters of the solution was placed in each of five 10.0 ml volumetric flasks. Then, 0.01 ml of 1 N HCI was added to each flask and each solution was diluted with ethanol to 10.0 ml. Each solution was originally colorless but became pinkish and lost its photochromic effect once the HCI was added. To four of the solutions was added about 3 mg of either Tinuvin 770, Tinuvin 765, Cyasorb 1084 or UV-Chek AM-205. The solutions containing the Tinuvin and Cyasorb compounds reverted to colorless solutions and regained their photochromic effect, while the other solutions remained pinkish and showed no photochromic effect.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Glass Compositions (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Medicinal Preparation (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86101289T ATE38391T1 (de) | 1985-01-31 | 1986-01-31 | Verfahren zur verbesserung der lichtermuedungsbestaendigkeit einer photochromen zusammensetzung und photochrome zusammensetzung. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US696452 | 1976-06-15 | ||
| US69645285A | 1985-01-31 | 1985-01-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0195898A1 EP0195898A1 (en) | 1986-10-01 |
| EP0195898B1 true EP0195898B1 (en) | 1988-11-02 |
Family
ID=24797122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86101289A Expired EP0195898B1 (en) | 1985-01-31 | 1986-01-31 | A method of increasing the light fatigue resistance of a photochromic composition and photochromic composition |
Country Status (6)
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU616650B2 (en) * | 1987-02-02 | 1991-11-07 | Toray Industries, Inc. | Spirooxazine photochromic compounds and resins |
| JPH0794657B2 (ja) * | 1987-10-16 | 1995-10-11 | 日産自動車株式会社 | フォトクロミック感光性材料 |
| IT1223067B (it) * | 1987-11-05 | 1990-09-12 | Enichem Sintesi | Composto fotocromatico ed articoli fotocromatici che lo contengono |
| US5180524A (en) * | 1987-11-05 | 1993-01-19 | Enichem Synthesis S.P.A. | Photochromatic composition and photochromatic articles which contain it |
| US5017225A (en) * | 1987-12-02 | 1991-05-21 | Japan Capsular Products Inc. | Microencapsulated photochromic material, process for its preparation and a water-base ink composition prepared therefrom |
| JP2545606B2 (ja) * | 1988-07-05 | 1996-10-23 | 呉羽化学工業株式会社 | フォトクロミック化合物およびフォトクロミック組成物 |
| GB8828091D0 (en) * | 1988-12-01 | 1989-01-05 | Traqson Ltd | Security marking |
| US5225113A (en) * | 1989-02-10 | 1993-07-06 | Enichem Synthesis S.P.A. | Photochromatic composition endowed with light fatigue resistance and photochromatic articles which contain it |
| IT1230711B (it) * | 1989-02-10 | 1991-10-29 | Enichem Sintesi | Composizione fotocromatica dotata di resistenza a fatica alla luce e articoli fotocromatici che la contengono. |
| JP2755444B2 (ja) * | 1989-09-28 | 1998-05-20 | 株式会社トクヤマ | クロメン組成物 |
| AU637868B2 (en) * | 1990-07-04 | 1993-06-10 | Lintec Corporation | Photochromic composition |
| EP0612796A1 (en) * | 1993-02-23 | 1994-08-31 | Ciba-Geigy Ag | Stabilisation of organic pigments |
| EP0612816B1 (en) * | 1993-02-23 | 1999-11-17 | Ciba SC Holding AG | Stabilisation of pyrrolopyrrole pigments |
| WO2008043848A2 (en) * | 2006-10-12 | 2008-04-17 | Opco Gmbh | Protective film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD156372A1 (de) * | 1981-02-13 | 1982-08-18 | Manfred Reichenbaecher | Photochrome medien unter verwendung von 1,4-2h-oxazinen und spirophenanthro-1,4-2h-oxazinen |
| US4440672A (en) * | 1982-03-22 | 1984-04-03 | American Optical Corporation | Photochromic composition resistant to fatigue |
-
1986
- 1986-01-21 CA CA000499989A patent/CA1268034A/en not_active Expired - Lifetime
- 1986-01-30 BR BR8600381A patent/BR8600381A/pt not_active IP Right Cessation
- 1986-01-31 EP EP86101289A patent/EP0195898B1/en not_active Expired
- 1986-01-31 JP JP61020026A patent/JPS61241383A/ja active Granted
- 1986-01-31 AT AT86101289T patent/ATE38391T1/de active
- 1986-01-31 DE DE8686101289T patent/DE3661076D1/de not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3661076D1 (en) | 1988-12-08 |
| JPS61241383A (ja) | 1986-10-27 |
| JPH0343315B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1991-07-02 |
| EP0195898A1 (en) | 1986-10-01 |
| ATE38391T1 (de) | 1988-11-15 |
| BR8600381A (pt) | 1986-10-14 |
| CA1268034A (en) | 1990-04-24 |
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