WO2011010307A1 - Improved color changing polymer-based article - Google Patents
Improved color changing polymer-based article Download PDFInfo
- Publication number
- WO2011010307A1 WO2011010307A1 PCT/IL2010/000577 IL2010000577W WO2011010307A1 WO 2011010307 A1 WO2011010307 A1 WO 2011010307A1 IL 2010000577 W IL2010000577 W IL 2010000577W WO 2011010307 A1 WO2011010307 A1 WO 2011010307A1
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- WO
- WIPO (PCT)
- Prior art keywords
- article
- color changing
- derivatives
- chemical compound
- color
- Prior art date
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Classifications
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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
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
Definitions
- the first one is the high price of products due to the expensive method of production.
- the second one is the technological limitations existing in using some commercial polymers that in term limit the possible uses of such products. These problems could be overcome by using injection molding or extrusion. These methods will also enable the use of polymers such as polycarbonate, PMMA, and polyurethane which are stronger and much cheaper, and will enable production of more photochromic applications that demand the use of such polymers.
- one of the known applications of photochromic technology is color changing lenses.
- the present invention enables to achieve the same performance as in cast molding but with a much lower cost, by adding special additives to non expensive commercial polymers, and using injection as the production method.
- the option to use many polymers will also enable manufacturing of strong color changing lenses as an example, for applications such as protective and sport.
- the layer that contains the photo changing compound is the outer layer of the lens; this makes the lens very sensitive to scratch.
- a polymer-based color changing article manufactured by injection, extrusion or similar methods comprising:
- At least one polymeric color changing enhancer additive distributed within said polymer matrix wherein said at least one polymeric color changing enhancer additive does not change its optical properties
- At least one chemical compound capable of reversible changing its original color due to a photochemical reaction at least one chemical compound capable of reversible changing its original color due to a photochemical reaction.
- said substantially transparent polymer matrix is selected from a group of polymers such as polyolefines, polystyrenes, polyacrylate derivatives, polyvinyl derivatives, polycarbonate derivatives, polyester derivatives, cellulose derivatives, taken alone or in any combination thereof.
- said at least one polymeric color changing enhancer additive is selected from a group of additives such as aliphatic esters, aromatic esters, taken alone or in any combination thereof.
- said at least one chemical compound is selected from a group of compounds such as spiropyranes, spiroxazines, naphthopyrans, taken alone or in any combination thereof.
- the article comprises a color agent.
- the article comprises a UV absorber. Furthermore and in accordance with another preferred embodiment of the present invention, the article comprises a stabilizer.
- said at least one chemical compound establishes 0.02 to 1 weight percent of the article.
- At least one polymeric color changing enhancer additive establishes 1 to 50 weight percent of the article.
- said at least one chemical compound can stand a manufacturing temperature up to 260 degrees Celsius.
- said photochemical reaction is a UV reaction.
- the article can be used for applications such as lenses, color changing protective shields or sheets for controlling the intensity of light irradiation within a room, car, greenhouse, games, toys, memorabilia, packages for light sensitive food, beverages, drugs.
- applications such as lenses, color changing protective shields or sheets for controlling the intensity of light irradiation within a room, car, greenhouse, games, toys, memorabilia, packages for light sensitive food, beverages, drugs.
- Figure 1 presents the general formula of Spiroxazines derivatives to be used in accordance with a preferred embodiment of the present invention.
- Figure 2 presents the general formula of Spiropyrans derivatives to be used in accordance with a preferred embodiment of the present invention.
- Figure 3 presents the chemical reaction of the derivatives represented in
- Figures 1 and 2 responsible for the change of color.
- Figure 4 presents the general formula of Naphthopyrans derivatives to be used in accordance with a preferred embodiment of the present invention.
- Figure 5 represents a general formula of aromatic ester to be used in accordance with a preferred embodiment of the present invention.
- the article should be capable of undergoing photochemical reaction in response to the UV radiation which will cause significant change in the visible range transmission.
- the compound should be able to undergo direct and reverse photochemical reaction, without significant decrease performance after continued exposure for at least six month in the sun.
- Fig. 4 Naphthopyrans derivatives represented by the general formula shown in Fig. 4.
- R 1 , R 2 , R3> R4, R5, Re represent independently an alkyl group, an alkoxy group, a nitro group or a halogen.
- R 3 - R 4 , R 5 - R 6 can also represent independently only a sole group, like an aromatic group, an alkoxy or thioaromatic group, for example as described in Van Germert, B MoI. Cryst. Liq. Cryst., 1997, Vol.297, p.131.
- the chemical reaction responsible for the change in color is presented with reference to Fig. 3
- the initially white colored article was changed into blue color after exposure to the sun light for a few seconds.
- the color faded in about a few minutes after the article was removed from the sunlight.
- the initially colorless article was changed into blue color after exposure to the sun light for a few seconds.
- the color changing articles of the present invention are made of an optically transparent polymeric material (base matrix) chosen from the group comprising polyolefin's, polystyrenes, polyacrylates, polyvinyl derivatives, polyester derivatives, cellulose derivatives etc. taken alone or in any combination thereof.
- the base composition consists also of special polymeric color changing enhancer additive such as aliphatic or aromatic esters.
- the base composition can comprise also stabilizers and UV absorbers and if needed, a color agent to increase or to change the initial or final color.
- the preferred manufacturing method for the articles production is injection molding or extrusion.
- Example of a stabilizer is nickel complex such as nickel ditiocarbomate
- Example of an absorber is 2-hydroxy-4-(N- octoxy)benzophenone.
- organic color agents suitable for this purpose include Phtalocyanine, Quinacridone, Isoindolinone, Perylene, Anthraquinone, etc.
- color changing articles corresponding to the present invention are various and can be also contemplated.
- lenses, color changing protective shields or sheets which can control the intensity of sun radiation within a room, car, greenhouse etc.
- Another example could be in the category of games, toys or memorabilia.
- further possible application of the invention can be packages for light sensitive food, beverages, drugs etc. so as to prevent their exposure to UV radiation or high intensive visible radiation outside, while allowing inspection of the interior by transparency or the package or part of it when the product is in indoor .
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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)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
A polymer-based color changing article manufactured by injection, extrusion or similar methods that comprises transparent polymer matrix, polymeric color changing enhancer additive distributed within the polymer matrix that does not change its optical properties and a chemical compound capable of reversible changing its original color due to a photochemical reaction. The polymer-based color changing article can be used for applications such as lenses, color changing protective shields or sheets for controlling the intensity of light irradiation within a room, car, greenhouse, games, toys, memorabilia, packages for light sensitive food, beverages, and drugs.
Description
IMPROVED COLOR CHANGING POLYMER-BASED ARTICLE Background of the Invention The ability of a chemical compound to change color when it is irradiated with electromagnetic radiation (particular ultraviolet range), and then returning to its original color when the irradiation is terminated, is referred to as photochromism. There are many applications that can make use of such compounds, for example film coating for windows, packages, optical objects, lenses, toys, etc.
There are two main obstacles in the way of mass production and use of such applications. The first one is the high price of products due to the expensive method of production. The second one is the technological limitations existing in using some commercial polymers that in term limit the possible uses of such products. These problems could be overcome by using injection molding or extrusion. These methods will also enable the use of polymers such as polycarbonate, PMMA, and polyurethane which are stronger and much cheaper, and will enable production of more photochromic applications that demand the use of such polymers. For example, one of the known applications of photochromic technology is color changing lenses.
The technology used today for manufacturing of color changing lenses is polymerization of special acrylic monomers rather than injection. This method is very slow and expensive. Since it involves cast of liquid expensive monomers in glass molds, and curing for 24 hours in oven at 80 deg. These cause the price to be high and hence the use of such lenses to be limited.
The reason why injection is not in use today for this application is due to the poor results, mainly slow color change and small change of light transmission.
The present invention enables to achieve the same performance as in cast molding but with a much lower cost, by adding special additives to non expensive commercial polymers, and using injection as the production method. The option to use many polymers will also enable manufacturing of
strong color changing lenses as an example, for applications such as protective and sport. There are patents disclosing color changing lenses made by injection molding. These patents disclosing production of lenses using a complex structure, mainly film attach to the injected lens. Examples of these patents are:
US patents no 5531940, 5998520, 6065836, 7314590, 7350917.
WO patents no. 2001/049478, 2003/078148, 2004/011235, and 2008/133342.
The main problems associated with these patents are:
1. The layer that contains the photo changing compound is the outer layer of the lens; this makes the lens very sensitive to scratch.
2. Due to the small thickness of the active layer, the require concentration of photo changing compound is much larger then in molding, which makes them more expensive.
3. Since the color change compound is very sensitive to heat, and most of the heat is concentrated in the coated layer, the life span of such lenses is much less compared to the injected lenses.
There are also known patents disclosing color changing film/toys made by injection/ extrusion molding. For example, US Patents no. 5,166,345, 6846934. However, there is a use of complex and expensive color changing compounds that have limited results.
Summary of the Invention It is an object of the present invention to provide a simple, economical, and efficient way to manufacture improved color changing articles by injection or extrusion.
In order to make the color changing effect significant while using the conventional color changing compounds, there is a need for a specific matrix composition containing special color changing polymeric additive (polymeric color changing enhancer additive) compatible to the polymer in use.
The particular compounds are chosen so they can withstand high temperature, in order to enable employing many types of polymers, and to use industrial fabrication methods suitable for mass production.
It is therefore provided in accordance with a preferred embodiment of the present invention a polymer-based color changing article manufactured by injection, extrusion or similar methods comprising:
substantially transparent polymer matrix;
at least one polymeric color changing enhancer additive distributed within said polymer matrix wherein said at least one polymeric color changing enhancer additive does not change its optical properties;
at least one chemical compound capable of reversible changing its original color due to a photochemical reaction.
Furthermore and in accordance with another preferred embodiment of the present invention, said substantially transparent polymer matrix is selected from a group of polymers such as polyolefines, polystyrenes, polyacrylate derivatives, polyvinyl derivatives, polycarbonate derivatives, polyester derivatives, cellulose derivatives, taken alone or in any combination thereof.
Furthermore and in accordance with another preferred embodiment of the present invention, said at least one polymeric color changing enhancer additive is selected from a group of additives such as aliphatic esters, aromatic esters, taken alone or in any combination thereof.
Furthermore and in accordance with another preferred embodiment of the present invention, said at least one chemical compound is selected from a group of compounds such as spiropyranes, spiroxazines, naphthopyrans, taken alone or in any combination thereof.
Furthermore and in accordance with another preferred embodiment of the present invention, the article comprises a color agent.
Furthermore and in accordance with another preferred embodiment of the present invention, the article comprises a UV absorber.
Furthermore and in accordance with another preferred embodiment of the present invention, the article comprises a stabilizer.
Furthermore and in accordance with another preferred embodiment of the present invention, said at least one chemical compound establishes 0.02 to 1 weight percent of the article.
Furthermore and in accordance with another preferred embodiment of the present invention, at least one polymeric color changing enhancer additive establishes 1 to 50 weight percent of the article.
Furthermore and in accordance with another preferred embodiment of the present invention, said at least one chemical compound can stand a manufacturing temperature up to 260 degrees Celsius.
Furthermore and in accordance with another preferred embodiment of the present invention, said photochemical reaction is a UV reaction.
In addition and in accordance with another preferred embodiment of the present invention, the article can be used for applications such as lenses, color changing protective shields or sheets for controlling the intensity of light irradiation within a room, car, greenhouse, games, toys, memorabilia, packages for light sensitive food, beverages, drugs. Brief description of the drawings
In order to better understand the present invention and appreciate its practical applications, the following Figures are attached and referenced herein. Like components are denoted by like reference numerals.
It should be noted that the figures are given as examples and preferred embodiments only and in no way limit the scope of the present invention as defined in the appending Description and Claims.
Figure 1 presents the general formula of Spiroxazines derivatives to be used in accordance with a preferred embodiment of the present invention.
Figure 2 presents the general formula of Spiropyrans derivatives to be used in accordance with a preferred embodiment of the present invention. Figure 3 presents the chemical reaction of the derivatives represented in
Figures 1 and 2 responsible for the change of color.
Figure 4 presents the general formula of Naphthopyrans derivatives to be used in accordance with a preferred embodiment of the present invention.
Figure 5 represents a general formula of aromatic ester to be used in accordance with a preferred embodiment of the present invention.
Detailed description of the preferred embodiments
It has been empirically established that the polymer-based articles of the present invention should satisfy the following criteria in order to advantageously improve the existing articles:
1. The article should be capable of undergoing photochemical reaction in response to the UV radiation which will cause significant change in the visible range transmission.
2. The compound should be able to undergo direct and reverse photochemical reaction, without significant decrease performance after continued exposure for at least six month in the sun.
3. The color changing compound and all other additives should withstand manufacturing temperature of up to 2600C. Some non-exhaustive representative examples of various compositions comprising suitable photochromic compounds are listed below:
a) Spiroxazines and Spiropyrans derivatives represented by the general formula shown in Fig.1 and Fig. 2. In the general formulas, R1, R2, R3, R4, Rs, Re, R7 represent independently an alkyl group, an aromatic group, an alkoxy group, a nitro group or a halogen. An example of the formulas is described in Nori, Y. C. Can. J. Chem. , 61 , 300 (1983). The chemical reaction responsible for the change in color is presented with reference to Fig.3.
b) Naphthopyrans derivatives represented by the general formula shown in Fig. 4. In the above formula, X=O, S, N-R1, (CH2)n and n= 0, 1 , 2, etc. R1, R2, R3> R4, R5, Re represent independently an alkyl group, an alkoxy group, a nitro group or a halogen. R3- R4, R5- R6 can also represent independently only a sole group, like an aromatic group, an alkoxy or thioaromatic group, for example as described in Van Germert, B MoI. Cryst. Liq. Cryst., 1997, Vol.297, p.131. The chemical reaction responsible for the change in color is presented with reference to Fig. 3
Example 1 :
An article with a 0.05% weight color changing compound Spiro[2H- indole-2,3'-[3H]naphth[2,1 -b][1 ,4]oxazine], 6'-(2,3-dihydro-1 H-indol-1 -yl)-1 ,3- dihydro-1 ,3,3-trimethyl, and 1% weight of UV stabilizer nickel dithiocarbamate and 10% Elvaloy 3427 were added to CH207 PMMA. The mixture were then compounded at 2200C, and then injected to obtain the desired article.
The initially white colored article was changed into blue color after exposure to the sun light for a few seconds. The color faded in about a few minutes after the article was removed from the sunlight.
Example 2:
A lens with a 0.5% weight of color changing compound Spiro[2H-indole-
2,3'-[3H]naphth[2,1 -b][1 ,4]oxazine], 6'-(2,3-dihydro-1 H-indol-1 -yl)-1 ,3-dihydro- 1 ,3,3-trimethyl, and 0.05% weight of UV stabilizer nickel dithiocarbamate and
0.05% weight and 1% SUN were added to the PC markrolon 2207 by
compounding at 240° C with subsequent injection molding to obtain the desired toy form :
The initially colorless article was changed into blue color after exposure to the sun light for a few seconds. The color faded in a minute after the article was removed from the sun light.
In practice, the color changing articles of the present invention are made of an optically transparent polymeric material (base matrix) chosen from the group comprising polyolefin's, polystyrenes, polyacrylates, polyvinyl derivatives, polyester derivatives, cellulose derivatives etc. taken alone or in any combination thereof. The base composition consists also of special polymeric color changing enhancer additive such as aliphatic or aromatic esters. The base composition can comprise also stabilizers and UV absorbers and if needed, a color agent to increase or to change the initial or final color. The preferred manufacturing method for the articles production is injection molding or extrusion. Example of a stabilizer is nickel complex such as nickel ditiocarbomate, Example of an absorber is 2-hydroxy-4-(N- octoxy)benzophenone. Examples of such organic color agents suitable for this purpose include Phtalocyanine, Quinacridone, Isoindolinone, Perylene, Anthraquinone, etc.
It should be appreciated that the present invention is not limited by the above-described embodiments and that changes and modifications can be made by one ordinarily skilled in the art without deviation from the scope of the invention as will be defined below in the appended claims.
Applications of the color changing articles corresponding to the present invention are various and can be also contemplated. For example, one can contemplate, lenses, color changing protective shields or sheets which can control the intensity of sun radiation within a room, car, greenhouse etc. Another example could be in the category of games, toys or memorabilia.
Still, further possible application of the invention can be packages for light sensitive food, beverages, drugs etc. so as to prevent their exposure to UV radiation or high intensive visible radiation outside, while allowing
inspection of the interior by transparency or the package or part of it when the product is in indoor .
It should be appreciated that features disclosed in the foregoing description, and/or in the following claims, and/or examples, may both separately and in any combination thereof, be material for realizing the present invention in diverse forms thereof.
Claims
1. A polymer-based color changing article manufactured by injection, extrusion or similar methods comprising:
substantially transparent polymer matrix;
at least one polymeric color changing enhancer additive distributed within said polymer matrix wherein said at least one polymeric color changing enhancer additive does not change its optical properties;
at least one chemical compound capable of reversible changing its original color due to a photochemical reaction.
2. The article as claimed in Claim 1 , wherein said substantially transparent polymer matrix is selected from a group of polymers such as polyolefines, polystyrenes, polyacrylate derivatives, polyvinyl derivatives, polycarbonate derivatives, polyester derivatives, cellulose derivatives, taken alone or in any combination thereof.
3. The article as claimed in Claim 1 , wherein said at least one polymeric color changing enhancer additive is selected from a group of additives such as aliphatic esters, aromatic esters, taken alone or in any combination thereof.
4. The article as claimed in Claim 1 , wherein said at least one chemical compound is selected from a group of compounds such as spiropyranes, spiroxazines, naphthopyrans, taken alone or in any combination thereof.
5. The article as claimed in Claim 1 , further comprising a color agent.
6. The article as claimed in Claim 1 , further comprising a UV absorber.
7. The article as claimed in Claim 1 , further comprising a stabilizer.
8. The article as claimed in Claim 1 , wherein said at least one chemical compound establishes 0.02 to 1 weight percent of the article.
9. The article as claimed in Claim 1 , wherein at least one polymeric color changing enhancer additive establishes 1 to 50 weight percent of the article.
10. The article as claimed in Claim 1 , wherein said at least one chemical compound can stand a manufacturing temperature up to 260 degrees
Celsius.
11. The article as claimed in Claim 1 , wherein said photochemical reaction is a UV reaction.
12. The article as claimed in Claim 1 , wherein the article can be used for applications such as lenses, color changing protective shields or sheets for controlling the intensity of light irradiation within a room, car, greenhouse, games, toys, memorabilia, packages for light sensitive food, beverages, drugs.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/386,739 US20120119170A1 (en) | 2009-07-24 | 2010-07-21 | Color changing polymer-based article |
| EP10802024A EP2457124A4 (en) | 2009-07-24 | 2010-07-21 | Improved color changing polymer-based article |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22816309P | 2009-07-24 | 2009-07-24 | |
| US61/228,163 | 2009-07-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011010307A1 true WO2011010307A1 (en) | 2011-01-27 |
Family
ID=43498824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IL2010/000577 WO2011010307A1 (en) | 2009-07-24 | 2010-07-21 | Improved color changing polymer-based article |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20120119170A1 (en) |
| EP (1) | EP2457124A4 (en) |
| WO (1) | WO2011010307A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140084498A1 (en) * | 2012-09-22 | 2014-03-27 | Kuo-Ching Chiang | Lens with filter and method of manufacturing thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439512A (en) * | 1975-12-05 | 1984-03-27 | La Cellophane | Chromogenic compositions containing stabilized phenolic coupler compounds, recording materials and processes utilizing same |
| US5166345A (en) | 1987-02-02 | 1992-11-24 | Toray Industries, Inc. | Photochromic compound |
| 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 |
| US5531940A (en) | 1993-12-10 | 1996-07-02 | Innotech, Inc. | Method for manufacturing photochromic lenses |
| US5998520A (en) | 1997-07-02 | 1999-12-07 | Bayer Corporation | Photochromic compositions having improved fade rate |
| US6065836A (en) | 1998-07-30 | 2000-05-23 | Bayer Corporation | Photochromic ophthalmic lens |
| WO2001049478A2 (en) | 1999-12-30 | 2001-07-12 | Bayer Corporation | A process for preparing a photochromic lens |
| WO2003078148A1 (en) | 2002-03-13 | 2003-09-25 | Vision/Ease Lens, Inc. | Injection molding of lens |
| WO2004011235A1 (en) | 2002-07-31 | 2004-02-05 | Bmc Industries, Inc. | Polyurethane laminates for photochromic lenses |
| US6846934B2 (en) | 2001-03-06 | 2005-01-25 | Korea Research Institute Of Chemical Technology | Photochromic diarylethene substituted with isoxazole group |
| US6863720B2 (en) * | 2001-06-08 | 2005-03-08 | Matsui Shikiso Chemical Co., Ltd. | Thermosensitive color-changing dry offset ink and a printed material using the same |
| US20050274055A1 (en) | 2004-06-09 | 2005-12-15 | Cook Roger B | Color-changing fishing equipment |
| US20070269740A1 (en) * | 2006-05-22 | 2007-11-22 | Blank David H | Methods of marking and related structures and compositions |
| US7314590B2 (en) | 2005-09-20 | 2008-01-01 | Bayer Materialscience Llc | Method of preparing a coated molded plastic article |
| US7316875B2 (en) * | 2005-05-06 | 2008-01-08 | Xerox Corporation | Photochromic paper with improved bistability |
| US7350917B2 (en) | 2004-02-02 | 2008-04-01 | Mgc Filseet Co Ltd | Light control plastic lens, coated sheet-like light control element for the lens production, and a production method for light control plastic lens |
| WO2008133342A1 (en) | 2007-04-25 | 2008-11-06 | Teijin Limited | Polycarbonate resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010019110A1 (en) * | 1997-09-16 | 2001-09-06 | Ori Faran | Dosimeter for sun radiation |
| AU6485799A (en) * | 1998-11-02 | 2000-05-22 | Skyrad Ltd. | Photochromic articles |
| JP2007246870A (en) * | 2006-03-18 | 2007-09-27 | Kashiro Murata | Photochromic material |
-
2010
- 2010-07-21 US US13/386,739 patent/US20120119170A1/en not_active Abandoned
- 2010-07-21 WO PCT/IL2010/000577 patent/WO2011010307A1/en active Application Filing
- 2010-07-21 EP EP10802024A patent/EP2457124A4/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439512A (en) * | 1975-12-05 | 1984-03-27 | La Cellophane | Chromogenic compositions containing stabilized phenolic coupler compounds, recording materials and processes utilizing same |
| US5166345A (en) | 1987-02-02 | 1992-11-24 | Toray Industries, Inc. | Photochromic compound |
| 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 |
| US5531940A (en) | 1993-12-10 | 1996-07-02 | Innotech, Inc. | Method for manufacturing photochromic lenses |
| US5998520A (en) | 1997-07-02 | 1999-12-07 | Bayer Corporation | Photochromic compositions having improved fade rate |
| US6065836A (en) | 1998-07-30 | 2000-05-23 | Bayer Corporation | Photochromic ophthalmic lens |
| WO2001049478A2 (en) | 1999-12-30 | 2001-07-12 | Bayer Corporation | A process for preparing a photochromic lens |
| US6846934B2 (en) | 2001-03-06 | 2005-01-25 | Korea Research Institute Of Chemical Technology | Photochromic diarylethene substituted with isoxazole group |
| US6863720B2 (en) * | 2001-06-08 | 2005-03-08 | Matsui Shikiso Chemical Co., Ltd. | Thermosensitive color-changing dry offset ink and a printed material using the same |
| WO2003078148A1 (en) | 2002-03-13 | 2003-09-25 | Vision/Ease Lens, Inc. | Injection molding of lens |
| WO2004011235A1 (en) | 2002-07-31 | 2004-02-05 | Bmc Industries, Inc. | Polyurethane laminates for photochromic lenses |
| US7350917B2 (en) | 2004-02-02 | 2008-04-01 | Mgc Filseet Co Ltd | Light control plastic lens, coated sheet-like light control element for the lens production, and a production method for light control plastic lens |
| US20050274055A1 (en) | 2004-06-09 | 2005-12-15 | Cook Roger B | Color-changing fishing equipment |
| US7316875B2 (en) * | 2005-05-06 | 2008-01-08 | Xerox Corporation | Photochromic paper with improved bistability |
| US7314590B2 (en) | 2005-09-20 | 2008-01-01 | Bayer Materialscience Llc | Method of preparing a coated molded plastic article |
| US20070269740A1 (en) * | 2006-05-22 | 2007-11-22 | Blank David H | Methods of marking and related structures and compositions |
| WO2008133342A1 (en) | 2007-04-25 | 2008-11-06 | Teijin Limited | Polycarbonate resin composition |
Non-Patent Citations (3)
| Title |
|---|
| NORI, Y. C., CAN. J. CHEM., vol. 61, 1983, pages 300 |
| See also references of EP2457124A4 * |
| VAN GEMERT, B MOL. CRYST. LIQ. CRYST., vol. 297, 1997, pages 131 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2457124A4 (en) | 2012-12-12 |
| EP2457124A1 (en) | 2012-05-30 |
| US20120119170A1 (en) | 2012-05-17 |
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