WO1998003890A1 - Stabilized matrix for photochromic articles - Google Patents
Stabilized matrix for photochromic articles Download PDFInfo
- Publication number
- WO1998003890A1 WO1998003890A1 PCT/US1997/012759 US9712759W WO9803890A1 WO 1998003890 A1 WO1998003890 A1 WO 1998003890A1 US 9712759 W US9712759 W US 9712759W WO 9803890 A1 WO9803890 A1 WO 9803890A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photochromic
- coating
- polyol
- polyisocyanate
- matrix
- Prior art date
Links
- 239000011159 matrix material Substances 0.000 title claims abstract description 34
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000004611 light stabiliser Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 25
- 229920005862 polyol Polymers 0.000 claims description 22
- 150000003077 polyols Chemical class 0.000 claims description 20
- 239000005056 polyisocyanate Substances 0.000 claims description 19
- 229920001228 polyisocyanate Polymers 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000008199 coating composition Substances 0.000 claims description 5
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical group CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000000087 stabilizing effect Effects 0.000 abstract description 5
- 239000000975 dye Substances 0.000 description 19
- 238000009472 formulation Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 etc.) Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- PJJBJBUPNNVMHB-UHFFFAOYSA-N 6,8,13,13a-tetrahydro-5h-isoquinolino[2,1-b]isoquinoline-1,4-diol Chemical compound C1C2=CC=CC=C2CN2C1C(C(O)=CC=C1O)=C1CC2 PJJBJBUPNNVMHB-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3293—Hydroxyamines containing heterocyclic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Definitions
- the invention relates to a photochromic article formed by applying a novel stabilizing polymeric matrix on a transparent substrate, which matrix includes a photochromic dye and an agent that stabilizes the dye against light being grafted onto the matrix.
- Organic photochromic materials are well known. They comprise a polymer matrix including a photochromic dye.
- One drawback of most of these materials is that their photochromic properties degrade too rapidly so that it is not possible to manufacture commercially usable articles from them, because their lifespan is insufficient. This degradation of the photochromic properties is due to a fatigue of the photochromic dye caused by light. Thus, there has been a need for many years for stable organic photochromic materials.
- the object of the invention is to satisfy this need.
- the invention is based on the idea of chemically combining a hindered amine to the macromolecules of a polymer matrix, rather than simply incorporating it in this matrix as in the above-mentioned patents.
- the invention relates to a photochromic article characterized in that it comprises a transparent substrate bearing at least one coating made of a polymer matrix including a photochromic dye and, as agent for stabilizing said dye against exposure to light, a hindered amine that is chemically bound to the macromolecules of the polymer matrix
- the invention relates to a stabilizing matrix for photochromic compounds, which matrix contains a functionalized hindered amine light stabilizer capable of reacting with an isocyanate group, and is linked to the polymer backbone by a covalent bond to form a stable functionalized (i.e., grafted) structure.
- the polymer matrix is a polyurethane.
- the invention relates to a photochromic organic material comprising a plastic substrate having formed thereon, a coating of a matrix composition, the composition being a polyurethane formulation comprising an isocyanate, a polyol, a hindered amine light stabilizer, and a photochromic dye.
- the invention also relates to a polymerizable coating composition that forms photochromically stabilized polyurethane, useful for the production of the photochromic article of the invention, comprising at least one polyisocyanate and at least one polyol, the polyisocyanate-polyol pair being chosen in such a manner that one of them presents one functional group more than the other, a photochromic dye preferably of the class of spiroxazines; a light stabilizer of the hindered amine-type, which amine comprises a reactive function with an isocyanate group; and optionally, a catalyst.
- polyisocyanate is understood to denote a compound comprising two isocyanate groups or more.
- polyol is understood to denote a compound comprising two hydroxyl groups or more, with the condition that the polyisocyanate and the polyol used comprise in total at least five isocyanate and hydroxyl groups. That is, the polyisocyanate must comprise at least three isocyanate groups when the polyol is a diol, and the polyol must comprise at least three hydroxyl groups when the polyisocyanate is a diisocyanate.
- polyol includes the polythiols.
- the hindered amine comprises a reactive hydroxyl group
- the polyisocyanate comprises three isocyanate groups
- the polyol is a diol.
- the invention in another aspect, relates to a method of making a photochromic organic article according to the invention, by: a) providing a transparent plastic substrate; b) applying a layer of a polymerizable composition of polyurethane matrix according to the invention on at least one surface of the substrate, and c) polymerizing the layer into a coating of photochromic polyurethane.
- the matrix comprises polyisocyanate, polyol, a hindered amine light stabilizer having a group which is capable of reacting with isocyanate to form a urethane function, a spirooxazine, a catalyst, and a solvent.
- the thickness of the coating may be in the range of 5-150, preferably, 10-100 microns.
- Photochromic materials in particular photochromic materials useful for ophthalmic applications such as lenses require good stability against photodegradation. Thus, such materials must be resistance to fatigue substantially over the useful life of the lens.
- One useful class of photochromic dyes useful for photochromic ophthalmic applications is spirooxazines. As stated earlier, one difficulty in making photochromic articles is the tendency of the photochromic dyes to lose photochromic activity in a polymer matrix with time.
- One class of stabilizers which have been suggested for such application is a hindered amine light stabilizer, or HALS. Particularly for ophthalmic applications, it is desirable to provide lenses having relatively thin photochromic coatings.
- hindered amine light stabilizers which alleviate the above problems.
- I have found that hindered amine light stabilizers having reactive functionalities are useful for the practice of the present invention.
- One particularly useful example of such functionalized HALS is tetramethyl piperidinol (available from ALDRICH), which contains an OH group which can react with an isocyanate to produce a urethane function.
- the -OH functionalized HALS is incorporated into a polyurethane formulation consisting of a mixture of polyisocyanate and polyol. Without intending to be bound by theory, I believe that the HALS reacts with the isocyanate groups and in the process, is linked to the polymer backbone by a covalent bond to form a grafted structure.
- the resulting matrix containing the grafted structure is highly stable and the HALS becomes integral to the matrix.
- the matrix is stabilized because the grafting prevents any aggregation or crystallization of the HALS.
- concentration of the grafted HALS is higher than with conventional free molecule HALS such as TINUVIN 770 for example (available from CIBA-GEIGY).
- the composition of the coating formulation is, in wt%: 30-55 wt% of polyisocyanate, 20-35 wt% of polyol, 2-10 wt% of reactive stabilizer with added functional group, 0.1-2 wt% of photochromic dye, 0-2 wt% of catalyst and 5-30 wt% of solvent. A proportion of 0.1-1 wt% of photochromic dye is preferred.
- the composition of the coating in weight percent is preferably: 30-60 polyisocyanate, 20-35 polyol, 2-10 tetramethyl piperidinol, and 0.1-1.0 photochromic dye.
- Nonlimiting examples of polyisocyanates that can be used in the invention are: meta- and para-xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- diphenyldiisocyanate, 4,4'-diphenyImethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and trimethyl-l,6-diisocyanatohexane.
- Nonlimiting examples of diols or polyols include: ethylene glycol, propylene glycol, 1,4-berbinediol, 1,6-hexanediol, 1,8-octanediol and similar compounds, cyclohexane dimethanol, glycol polyalkoyl ethers with a molecular weight of less than 10,000 (for example, polyethylene glycol, polypropylene glycol, etc.), polyester diols (for example, polycaprolactonediol), aromatic diols, polycarbonate diols, glycerol, trimethylolpropane, hexanetriol, pentaerythritol, polythiols, etc.
- Optional catalysts include all the catalysts which are conventionally used in the polyurethane formulations. Dibutyltin dilaurate and stannous octoate are used most routinely.
- Example 1 represents the invention, while Examples 2 and 3 are comparative compositions showing respectively, a formulation using a non-functionalized HALS, and without a stabilizer.
- CYTHANE 3160 an aliphatic polyisocyanate resin available from AMERICAN CYANAMID
- VARICROL BLUE D (a spirooxazine photochromic dye available from ENICHEM)
- a coating of about 100 microns of each of the above three photochromic formulations were applied to the surface of a piano lens made of CR39 R (a polybis(allylcarbonate) of diethylene glycol available from PPG Industries), and cured at 50 °C for 1 hour, and 130 °C for an additional hour.
- CR39 R a polybis(allylcarbonate) of diethylene glycol available from PPG Industries
- each coated sample After curing, the transmittance of each coated sample was measured. All three samples showed very high transmittances (>90%). Also, each sample had acceptable optical quality.
- the use of the inventive grafted (functionalized) stabilizer leads to improved photochromic performance after exposure to light, and also allows for the incorporation of a larger amount of stabilizer to the matrix without any significant detrimental effects on photochromicity since the grafted stabilizer does not migrate.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Eyeglasses (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Filters (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU39612/97A AU3961297A (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
US09/230,006 US6083427A (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
DE69724643T DE69724643T2 (en) | 1996-07-23 | 1997-06-26 | STABILIZED MATRIX FOR PHOTOCHROME ITEMS |
CA002257543A CA2257543A1 (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
JP50716898A JP4331265B2 (en) | 1996-07-23 | 1997-06-26 | Stabilization matrix for photochromic products |
EP97936985A EP0944689B1 (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
BR9710843A BR9710843A (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9609236A FR2751763B1 (en) | 1996-07-23 | 1996-07-23 | PHOTOCHROMIC ARTICLE, ITS MANUFACTURE AND COMPOSITION FOR ITS MANUFACTURE |
FR96/09236 | 1996-07-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998003890A1 true WO1998003890A1 (en) | 1998-01-29 |
Family
ID=9494364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/012759 WO1998003890A1 (en) | 1996-07-23 | 1997-06-26 | Stabilized matrix for photochromic articles |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0944689B1 (en) |
JP (1) | JP4331265B2 (en) |
KR (1) | KR20000067988A (en) |
AR (1) | AR007959A1 (en) |
AU (1) | AU3961297A (en) |
BR (1) | BR9710843A (en) |
CA (1) | CA2257543A1 (en) |
DE (1) | DE69724643T2 (en) |
ES (1) | ES2206745T3 (en) |
FR (1) | FR2751763B1 (en) |
TW (1) | TW347471B (en) |
WO (1) | WO1998003890A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001072851A1 (en) * | 2000-03-31 | 2001-10-04 | Sola International Holdings Limited | Photochromic article and method of preparation |
CN105934458A (en) * | 2014-02-03 | 2016-09-07 | 三井化学株式会社 | Polymerizable composition for optical material, and optical material and plastic lens obtained from said composition |
EP3122839A4 (en) * | 2014-03-25 | 2017-11-22 | SABIC Global Technologies B.V. | Color changing material |
EP3269774A4 (en) * | 2015-03-10 | 2018-10-31 | Tokuyama Corporation | Method for producing photochromic cured body |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001057106A1 (en) * | 2000-02-04 | 2001-08-09 | Ppg Industries Ohio, Inc. | Photochromic coated articles |
US8017720B2 (en) | 2005-12-16 | 2011-09-13 | Ppg Industries Ohio, Inc. | Sulfur-containing oligomers and high index polyurethanes prepared therefrom |
KR100567440B1 (en) * | 2002-12-09 | 2006-04-04 | 홍영표 | Method for preparing polyurethane containing photochromic compound |
US11149107B2 (en) | 2004-09-01 | 2021-10-19 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20090280329A1 (en) | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US11248083B2 (en) | 2004-09-01 | 2022-02-15 | Ppg Industries Ohio, Inc. | Aircraft windows |
US9464169B2 (en) | 2004-09-01 | 2016-10-11 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US11008418B2 (en) | 2004-09-01 | 2021-05-18 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US9598527B2 (en) | 2004-09-01 | 2017-03-21 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US11591436B2 (en) | 2004-09-01 | 2023-02-28 | Ppg Industries Ohio, Inc. | Polyurethane article and methods of making the same |
US20090280709A1 (en) | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US7553925B2 (en) | 2006-05-05 | 2009-06-30 | Ppg Industries Ohio, Inc. | Thioether functional oligomeric polythiols and articles prepared therefrom |
JP5863317B2 (en) * | 2010-09-29 | 2016-02-16 | 株式会社トクヤマ | Photochromic composition |
JP5967877B2 (en) * | 2011-03-11 | 2016-08-10 | 株式会社トクヤマ | Photochromic composition and optical article |
US9316765B2 (en) * | 2011-12-26 | 2016-04-19 | Tokuyama Corporation | Photochromic composition |
WO2019117305A1 (en) * | 2017-12-15 | 2019-06-20 | Mitsui Chemicals, Inc. | Polymerizable composition for optical materials and application of same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5391327A (en) * | 1992-09-25 | 1995-02-21 | Transitions Optical, Inc. | Photochromic compositions of improved fatigue resistance |
WO1995010790A1 (en) * | 1993-10-15 | 1995-04-20 | Ppg Industries, Inc. | High refractive index photochromic ophthalmic article |
US5498686A (en) * | 1991-08-22 | 1996-03-12 | Optische Werke G. Rodenstock | Optically transparent photochromic plastic material |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03192249A (en) * | 1989-12-21 | 1991-08-22 | Toray Ind Inc | Production of article having photochromic property |
JPH0816215B2 (en) * | 1990-06-18 | 1996-02-21 | 株式会社松井色素化学工業所 | Photochromic material |
JPH06184355A (en) * | 1992-12-16 | 1994-07-05 | Sumitomo Chem Co Ltd | Photochromic resin composition |
-
1996
- 1996-07-23 FR FR9609236A patent/FR2751763B1/en not_active Expired - Fee Related
-
1997
- 1997-06-26 EP EP97936985A patent/EP0944689B1/en not_active Expired - Lifetime
- 1997-06-26 JP JP50716898A patent/JP4331265B2/en not_active Expired - Fee Related
- 1997-06-26 CA CA002257543A patent/CA2257543A1/en not_active Abandoned
- 1997-06-26 BR BR9710843A patent/BR9710843A/en not_active Application Discontinuation
- 1997-06-26 WO PCT/US1997/012759 patent/WO1998003890A1/en not_active Application Discontinuation
- 1997-06-26 ES ES97936985T patent/ES2206745T3/en not_active Expired - Lifetime
- 1997-06-26 KR KR1019997000517A patent/KR20000067988A/en not_active Application Discontinuation
- 1997-06-26 DE DE69724643T patent/DE69724643T2/en not_active Expired - Fee Related
- 1997-06-26 AU AU39612/97A patent/AU3961297A/en not_active Abandoned
- 1997-07-11 TW TW086110040A patent/TW347471B/en active
- 1997-07-22 AR ARP970103294A patent/AR007959A1/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5498686A (en) * | 1991-08-22 | 1996-03-12 | Optische Werke G. Rodenstock | Optically transparent photochromic plastic material |
US5391327A (en) * | 1992-09-25 | 1995-02-21 | Transitions Optical, Inc. | Photochromic compositions of improved fatigue resistance |
WO1995010790A1 (en) * | 1993-10-15 | 1995-04-20 | Ppg Industries, Inc. | High refractive index photochromic ophthalmic article |
Non-Patent Citations (1)
Title |
---|
See also references of EP0944689A4 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001072851A1 (en) * | 2000-03-31 | 2001-10-04 | Sola International Holdings Limited | Photochromic article and method of preparation |
US6811830B2 (en) | 2000-03-31 | 2004-11-02 | Sola International Holdings, Ltd. | Photochromic article and method of preparation |
CN105934458A (en) * | 2014-02-03 | 2016-09-07 | 三井化学株式会社 | Polymerizable composition for optical material, and optical material and plastic lens obtained from said composition |
EP3103822A4 (en) * | 2014-02-03 | 2017-09-13 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, and optical material and plastic lens obtained from said composition |
EP3122839A4 (en) * | 2014-03-25 | 2017-11-22 | SABIC Global Technologies B.V. | Color changing material |
EP3269774A4 (en) * | 2015-03-10 | 2018-10-31 | Tokuyama Corporation | Method for producing photochromic cured body |
AU2016228367B2 (en) * | 2015-03-10 | 2019-11-07 | Tokuyama Corporation | Method for producing photochromic cured body |
US10526533B2 (en) | 2015-03-10 | 2020-01-07 | Tokuyama Corporation | Process for producing a photochromic cured body |
AU2016228367C1 (en) * | 2015-03-10 | 2020-04-09 | Tokuyama Corporation | Method for producing photochromic cured body |
Also Published As
Publication number | Publication date |
---|---|
ES2206745T3 (en) | 2004-05-16 |
EP0944689A4 (en) | 1999-09-29 |
TW347471B (en) | 1998-12-11 |
JP2000515904A (en) | 2000-11-28 |
FR2751763A1 (en) | 1998-01-30 |
DE69724643D1 (en) | 2003-10-09 |
AU3961297A (en) | 1998-02-10 |
CA2257543A1 (en) | 1998-01-29 |
EP0944689A1 (en) | 1999-09-29 |
FR2751763B1 (en) | 1998-10-09 |
EP0944689B1 (en) | 2003-09-03 |
KR20000067988A (en) | 2000-11-25 |
DE69724643T2 (en) | 2004-06-24 |
AR007959A1 (en) | 1999-11-24 |
BR9710843A (en) | 1999-08-17 |
JP4331265B2 (en) | 2009-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0944689B1 (en) | Stabilized matrix for photochromic articles | |
US6083427A (en) | Stabilized matrix for photochromic articles | |
US11795331B2 (en) | Curable photochromic compositions | |
AU718471B2 (en) | Photochromic polyurethane coating and articles having such a coating | |
US6733887B2 (en) | Photochromic coated high impact resistant articles | |
EP1495061B1 (en) | Photochromic compositions, preparation thereof and articles made therefrom or coated therewith | |
AU2006280850B2 (en) | Polythiourethane-based polymerizable composition and optical resin obtained from the same | |
CN108162536B (en) | Photochromic polyurethane composites | |
US20010050356A1 (en) | Photochromic organic resin composition | |
EP1301550B1 (en) | Method for preparing a photochromic polyurethane latex and application to ophthalmic optics | |
US9726785B2 (en) | Photochromic polyurethane laminate | |
KR100581771B1 (en) | Photochromic primer composition having high impact resistance and transparent material coated with the same | |
KR102600843B1 (en) | Optical adhesives, optical laminates, and lenses manufactured using them | |
US20040180211A1 (en) | Photochromic polyurethane film of improved fatigue resistance | |
CA3072251C (en) | Curable photochromic composition including a segmented polymer | |
CN1223724A (en) | Stabilized matrix for photochromic articles | |
CN115066472A (en) | Primer composition for optical article and laminate | |
ES2971851T3 (en) | Curable photochromic composition including a segmented polymer | |
KR20070097728A (en) | A reactive spironaphthoxazine compound, a photocromic polyurethane grafted with the spironaphthoxazine graft, a photocromic polyuretane coating membrane, and a photochromic optical article comprising the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 97195955.2 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU BR CA CN JP KR MX RU US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2257543 Country of ref document: CA Ref document number: 2257543 Country of ref document: CA Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09230006 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/A/1999/000831 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1019997000517 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1997936985 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1997936985 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1019997000517 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1997936985 Country of ref document: EP |
|
WWR | Wipo information: refused in national office |
Ref document number: 1019997000517 Country of ref document: KR |