EP0195898A1 - Verfahren zur Verbesserung der Lichtermüdungsbeständigkeit einer photochromen Zusammensetzung und photochrome Zusammensetzung - Google Patents

Verfahren zur Verbesserung der Lichtermüdungsbeständigkeit einer photochromen Zusammensetzung und photochrome Zusammensetzung Download PDF

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Publication number
EP0195898A1
EP0195898A1 EP86101289A EP86101289A EP0195898A1 EP 0195898 A1 EP0195898 A1 EP 0195898A1 EP 86101289 A EP86101289 A EP 86101289A EP 86101289 A EP86101289 A EP 86101289A EP 0195898 A1 EP0195898 A1 EP 0195898A1
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EP
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Prior art keywords
lower alkyl
hydrogen
photochromic
hindered amine
nickel
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Application number
EP86101289A
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English (en)
French (fr)
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EP0195898B1 (de
Inventor
Nori Y. C. Chu
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American Optical Corp
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American Optical Corp
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Priority to AT86101289T priority Critical patent/ATE38391T1/de
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    • 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 [indofine-2;3'-[3H] -napht [2,1-b] [1,4] 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 tight 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.
  • One class of organic photochromic compounds spiro - [indoline-2,3'-[3H]-naphth [2,1-b] [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 4,440,672.
  • 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 photocolorabil- i ty 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, is lower alkyl; and, b) an unconven- tonal 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 SO 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 be 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.
  • the hindered amine light stabilizer is di(1,2,2,6,B-pentamethyl-4-PiPeridinyl)-bytyl(3', 5'-diterbutyi-4-hydroxybenzyl) malonate, wherein R 1 , R 2 , R 4 , R s , R 6 , R 7 , R 9 , R 10 R 12 R 13 R 14 , R 15 , R 16 , and R 17 are methyl, R 11 is butyi, and R 3 and R, are methyl, sold under the tradename of Tinuvin 144, and obtained from the Ciba-Geigy Corporation.
  • 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-butyi- dithiocarbamate, 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 Nr 2+ complexes are normally used in polyolefins to provide protection from photo-degradation.
  • 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.
  • the preferred S.O. dyes for use in accordance with the invention are 1,3,3,4,5-pentamethyl-9'-methoxy-spiro - [indoline-2,3'-[3H]-naphfh [2,1-b] [1,4] oxazine; 1,3,3,5,6-pentamethyl-9'-methoxy-spirooxazine;
  • the preferred plastic hosts are cellulose acetate butyrate (CAB); CR-39TM , a diethylene glycol bis (allyl carbonate) obtained from PPG Industries, Inc.; LexanTM, a polycarbonate resin condensation product of bisphenol-A and phosgene, obtained from General Electric; Plexiglas TM , a polymethyl methacrylate obtained from the Rohm and Haas Company; polyvinyl chloride; and polyoleflns.
  • CAB cellulose acetate butyrate
  • CR-39TM a diethylene glycol bis (allyl carbonate) obtained from PPG Industries, Inc.
  • LexanTM a polycarbonate resin condensation product of bisphenol-A and phosgene, obtained from General Electric
  • Plexiglas TM a polymethyl methacrylate obtained from the Rohm and Haas Company
  • polyvinyl chloride polyoleflns.
  • 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/60mls) were 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-hexamethyl-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% cetyl 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.
  • 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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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Glass Compositions (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Medicinal Preparation (AREA)
EP86101289A 1985-01-31 1986-01-31 Verfahren zur Verbesserung der Lichtermüdungsbeständigkeit einer photochromen Zusammensetzung und photochrome Zusammensetzung Expired EP0195898B1 (de)

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 true EP0195898A1 (de) 1986-10-01
EP0195898B1 EP0195898B1 (de) 1988-11-02

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EP86101289A Expired EP0195898B1 (de) 1985-01-31 1986-01-31 Verfahren zur Verbesserung der Lichtermüdungsbeständigkeit einer photochromen Zusammensetzung und photochrome Zusammensetzung

Country Status (6)

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EP (1) EP0195898B1 (de)
JP (1) JPS61241383A (de)
AT (1) ATE38391T1 (de)
BR (1) BR8600381A (de)
CA (1) CA1268034A (de)
DE (1) DE3661076D1 (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0277639A2 (de) * 1987-02-02 1988-08-10 Toray Industries, Inc. Photochrome Verbindung
EP0313941A1 (de) * 1987-10-16 1989-05-03 Nissan Motor Co., Ltd. Photochromes Material
EP0316980A1 (de) * 1987-11-05 1989-05-24 ENICHEM SYNTHESIS S.p.A. Photochromische Zusammensetzung und diese Zusammensetzung enthaltende Gegenstände
EP0346484A1 (de) * 1987-12-02 1989-12-20 Japan Capsular Products, Inc. Mikroeingekapseltes photochromes material, verfahren zur herstellung und tintenzusammensetzung auf wasserbasis
EP0350009A1 (de) * 1988-07-05 1990-01-10 Kureha Kagaku Kogyo Kabushiki Kaisha Photochrome Verbindung und photochrome Zusammensetzung
WO1990006539A1 (en) * 1988-12-01 1990-06-14 Traqson Limited Security marking
EP0382294A1 (de) * 1989-02-10 1990-08-16 GREAT LAKES CHEMICAL ITALIA S.r.l. Lichtbeständige photochrome Zusammensetzung und diese enthaltende photochrome Gegenstände
EP0467552A1 (de) * 1990-07-04 1992-01-22 LINTEC Corporation Photochrome Zusammensetzungen
US5180524A (en) * 1987-11-05 1993-01-19 Enichem Synthesis S.P.A. Photochromatic composition and photochromatic articles which contain it
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
EP0612796A1 (de) * 1993-02-23 1994-08-31 Ciba-Geigy Ag Stabilisierung organischer Pigmente
EP0612816A1 (de) * 1993-02-23 1994-08-31 Ciba-Geigy Ag Stabilisierung von Pyrrolopyrrolpigmenten
WO2008043853A2 (en) * 2006-10-12 2008-04-17 Opco Gmbh Photochromic film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2755444B2 (ja) * 1989-09-28 1998-05-20 株式会社トクヤマ クロメン組成物

Citations (2)

* Cited by examiner, † Cited by third party
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
GB2117390A (en) * 1982-03-22 1983-10-12 American Optical Corp Photochromic composition resistant to light fatigue

Patent Citations (2)

* Cited by examiner, † Cited by third party
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
GB2117390A (en) * 1982-03-22 1983-10-12 American Optical Corp Photochromic composition resistant to light fatigue

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MODERN PLASTICS ENCYCLOPEDIA, 1983-1984, 5, Bristol LI, S.S. "Ultraviolet Stabilizers" pages 174-177 page 174, left column, lines 1-17 - middle column, line 35 - right column,line 22 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0277639A2 (de) * 1987-02-02 1988-08-10 Toray Industries, Inc. Photochrome Verbindung
EP0277639A3 (en) * 1987-02-02 1990-06-13 Toray Industries, Inc. Photochromic compound
EP0313941A1 (de) * 1987-10-16 1989-05-03 Nissan Motor Co., Ltd. Photochromes Material
EP0316980A1 (de) * 1987-11-05 1989-05-24 ENICHEM SYNTHESIS S.p.A. Photochromische Zusammensetzung und diese Zusammensetzung enthaltende Gegenstände
US5180524A (en) * 1987-11-05 1993-01-19 Enichem Synthesis S.P.A. Photochromatic composition and photochromatic articles which contain it
EP0346484A4 (en) * 1987-12-02 1990-09-05 Japan Capsular Products, Inc. Microencapsulated photochromic material, process for its preparation, and water-base ink composition prepared therefrom
EP0346484A1 (de) * 1987-12-02 1989-12-20 Japan Capsular Products, Inc. Mikroeingekapseltes photochromes material, verfahren zur herstellung und tintenzusammensetzung auf wasserbasis
EP0350009A1 (de) * 1988-07-05 1990-01-10 Kureha Kagaku Kogyo Kabushiki Kaisha Photochrome Verbindung und photochrome Zusammensetzung
WO1990006539A1 (en) * 1988-12-01 1990-06-14 Traqson Limited Security marking
EP0382294A1 (de) * 1989-02-10 1990-08-16 GREAT LAKES CHEMICAL ITALIA S.r.l. Lichtbeständige photochrome Zusammensetzung und diese enthaltende photochrome Gegenstände
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
EP0467552A1 (de) * 1990-07-04 1992-01-22 LINTEC Corporation Photochrome Zusammensetzungen
US5266447A (en) * 1990-07-04 1993-11-30 Lintec Corporation Photochromic composition
EP0612796A1 (de) * 1993-02-23 1994-08-31 Ciba-Geigy Ag Stabilisierung organischer Pigmente
EP0612816A1 (de) * 1993-02-23 1994-08-31 Ciba-Geigy Ag Stabilisierung von Pyrrolopyrrolpigmenten
WO2008043853A2 (en) * 2006-10-12 2008-04-17 Opco Gmbh Photochromic film
WO2008043853A3 (en) * 2006-10-12 2008-05-29 Opco Gmbh Photochromic film

Also Published As

Publication number Publication date
JPS61241383A (ja) 1986-10-27
CA1268034A (en) 1990-04-24
BR8600381A (pt) 1986-10-14
ATE38391T1 (de) 1988-11-15
JPH0343315B2 (de) 1991-07-02
DE3661076D1 (en) 1988-12-08
EP0195898B1 (de) 1988-11-02

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