CA2580765A1 - Acrylic glass having photochromic properties - Google Patents
Acrylic glass having photochromic properties Download PDFInfo
- Publication number
- CA2580765A1 CA2580765A1 CA002580765A CA2580765A CA2580765A1 CA 2580765 A1 CA2580765 A1 CA 2580765A1 CA 002580765 A CA002580765 A CA 002580765A CA 2580765 A CA2580765 A CA 2580765A CA 2580765 A1 CA2580765 A1 CA 2580765A1
- Authority
- CA
- Canada
- Prior art keywords
- polymethyl methacrylate
- sandwich
- intermediate layer
- element according
- sheets
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/54—Slab-like translucent elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to polymethyl methacrylate that has photochromic properties, to methods for producing it and to uses thereof.
Description
Acrylic glass having photochromic properties The invention relates to acrylic sheet with phototropic properties, production processes, and uses.
For some time there have been dyes which exhibit a light-dependent change in shade and intensity. The use of these dyes in plastics is known. However, the dyes cannot be incorporated into any desired plastics matrix. In order to become effective, the dye molecule has to be allowed sufficient freedom for the colour effect to be developed via isomerism. Polyurethanes are mostly used because they provide a suitable matrix for the dyes.
The hardness of polymethyl methacrylate makes it an unsuitable plastics matrix for these dyes, because it does not allow the dye molecules the necessary freedom of movement. The system becomes effective when rela-tively large amounts of plasticizers or of plasticizing comonomers are added. However, the material here becomes so soft that it no longer complies with the requirements for the respective applications.
It was therefore an object to produce a polymethyl methacrylate with phototropic properties.
The object has been achieved via polymethyl meth-acrylate sandwich elements comprising two polymethyl methacrylate sheets and an intermediate layer which comprises phototropic dyes.
Surprisingly, it has been found that by using a sandwich structure it is possible to produce polymethyl methacrylate (PMMA) with phototropic properties. The two outer PMMA sheets here provide the mechanical stability, and the soft intermediate layer permits introduction of phototropic dyes.
For some time there have been dyes which exhibit a light-dependent change in shade and intensity. The use of these dyes in plastics is known. However, the dyes cannot be incorporated into any desired plastics matrix. In order to become effective, the dye molecule has to be allowed sufficient freedom for the colour effect to be developed via isomerism. Polyurethanes are mostly used because they provide a suitable matrix for the dyes.
The hardness of polymethyl methacrylate makes it an unsuitable plastics matrix for these dyes, because it does not allow the dye molecules the necessary freedom of movement. The system becomes effective when rela-tively large amounts of plasticizers or of plasticizing comonomers are added. However, the material here becomes so soft that it no longer complies with the requirements for the respective applications.
It was therefore an object to produce a polymethyl methacrylate with phototropic properties.
The object has been achieved via polymethyl meth-acrylate sandwich elements comprising two polymethyl methacrylate sheets and an intermediate layer which comprises phototropic dyes.
Surprisingly, it has been found that by using a sandwich structure it is possible to produce polymethyl methacrylate (PMMA) with phototropic properties. The two outer PMMA sheets here provide the mechanical stability, and the soft intermediate layer permits introduction of phototropic dyes.
It has been found that the outer PMMA sheets can be modified with the known additives. Light stabilizers may preferably be incorporated. Particularly suitable additives are those which filter only short-wave UV
light, examples being bisoxanilines or compounds from the HALS (Hindered Amine Light Stabilizers) group.
The PMMA sheets may moreover comprise dyes which are permeable to UV light.
The intermediate layer has to be sufficiently soft to leave enough freedom for the dye molecules to produce the colour change via isomerism.
Surprisingly, it has been found that polymethyl meth-acrylates with plasticizers and/or with comonomers are suitable for the intermediate layer. Plasticizers which may be used are any of the commercially available additives, such as adipates, phthalates, phosphates or citrates. Plasticizers particularly preferably added are di-n-butyl adipate and diisobutyl phthalate.
Comonomers which may be used are a wide variety of PMMA-compatible monomers. Particularly suitable compounds are those from the class of the acrylates or of the higher-alkylated methacrylates.
It has been found that the intermediate layer can also be composed entirely of polyacrylates or of higher-alkylated polymethacrylates. Propyl, butyl and longer-chain methacrylates have been found to be particularly suitable.
Any of the known phototropic dyes may be introduced into the intermediate layer. It is preferable to use dyes from the group of the spironaphthoxazines and naphthopyrans. Particular preference is given to photo-chromic Reversacol dyes from J. Robinson (Huddersfield, England), e.g. Gray 219, Gray 208, Gray 306, Gray 195, Brown 105, Flamme 29 B, Sea Green 5, Velvet Blue, Sunflower, Graphite and Palatinate Purple.
The amount of these dyes added to the plastics matrix is a function of the layer thickness. A very small thickness requires a high concentration. By way of example, the amounts added of the dyes are from 0.001%
to 0.3% at a thickness of 3 mm. At very small layer : thicknesses, up to 10% of dyes may be added. It has been found that good phototropic properties are detectable when the thickness of the intermediate layer is from 0.01 to 5 mm. The best results were achieved with layer thicknesses of from 0.1 to 3 mm. Mixtures of various dyes may also be used.
It has been found that the inventive sandwich elements can be produced by various processes. A particularly suitable process is the cell casting process. The cell casting process here is used to produce the polymethyl methacrylate sheets separately. The temperature and time for heat-conditioning are set as a function of the thickness of the sheets. The conventional additives, e.g. UV filters, initiators, dyes or stabilizers, may be added. The intermediate layer is then cast with the appropriate additives, e.g. phototropic dyes and, if appropriate, plasticizers, between the polymethyl meth-acrylate sheets. The bond is produced via swelling processes. The PMMA sheets may be treated with cross-linking agents in order to regulate the swelling.
Another suitable process for producing the inventive sandwich elements is the internal coextrusion process.
EP1270176 describes a process for producing multilayer hollow-chamber profiled sheets. This process produces an upper and a lower layer from a plastics melt and a layer situated within the hollow-chamber profile and composed of a plastics melt by coextrusion of the plastics melt and use of an extrusion die, and then calibration of the resultant extrudate. The inventive sandwich elements can be produced by this process using an appropriately designed extrusion die.
The invention therefore also comprises the cell casting process and the internal coextrusion process for producing the inventive sandwich elements.
The polymethyl methacrylate sandwich elements with phototropic dyes are versatile. By way of example, they can be used for automatic shading systems in the construction sector, e.g. greenhouses, conservatories, glazing (e.g. skylights), display windows.
The examples given below are given to provide better illustration of the present invention, but are not intended to restrict the invention to the features disclosed herein.
Examples Example 1 Colourless acrylic sheet for outer panes of the sandwich element The following additives are dissolved, with stirring, in 998 parts of methyl methacrylate prepolymer (viscosity about 1000 cP):
1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) 1 part of glycol dimethacrylate Light stabilizers may also be optionally added in order to protect the photochromic inner layer.
Suitable products for this purpose are HALS products, such as Tinuvin 770, and UV absorbers which are particularly effective in the short-wavelength UV
region, e.g. Sanduvor VSU.
The mixture is vigorously stirred, charged to a silicate glass cell of 400 x 500 mm format with a 3 mm-thickness separating bead, and polymerized in a water bath for 16 h at 45 C. Completion of the polymerization takes place in a heat-conditioning cabinet for 4h at 115 C.
Example 2 Photochromic inner layer of the sandwich element:
The following additives are dissolved, with stirring, in 9988 parts of butyl methacrylate:
5 parts of 2,2'-azobis(isobutyronitrile) 5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) 1 part of Reversacol Sunflower Bt 278/13 (photochromic dye from James Robinson, England) 1 part of Reversacol Palatinate Purple (photochromic dye from James Robinson, England) The mixture is vigorously stirred, charged to a cell composed of colourless acrylic sheet from Experiment 1 with a 3 mm-thickness bead as separator, and poly-merized in a water bath for 22 h at 50 C.
This gives a transparent, slightly yellowish sheet with the high mechanical strength typical of poly-methacrylate. The result of irradiation with sunlight is that, depending on light intensity, the sheet becomes markedly more strongly coloured after from about 30 seconds to 2 minutes, and assumes a grey-brown to brown colour.
light, examples being bisoxanilines or compounds from the HALS (Hindered Amine Light Stabilizers) group.
The PMMA sheets may moreover comprise dyes which are permeable to UV light.
The intermediate layer has to be sufficiently soft to leave enough freedom for the dye molecules to produce the colour change via isomerism.
Surprisingly, it has been found that polymethyl meth-acrylates with plasticizers and/or with comonomers are suitable for the intermediate layer. Plasticizers which may be used are any of the commercially available additives, such as adipates, phthalates, phosphates or citrates. Plasticizers particularly preferably added are di-n-butyl adipate and diisobutyl phthalate.
Comonomers which may be used are a wide variety of PMMA-compatible monomers. Particularly suitable compounds are those from the class of the acrylates or of the higher-alkylated methacrylates.
It has been found that the intermediate layer can also be composed entirely of polyacrylates or of higher-alkylated polymethacrylates. Propyl, butyl and longer-chain methacrylates have been found to be particularly suitable.
Any of the known phototropic dyes may be introduced into the intermediate layer. It is preferable to use dyes from the group of the spironaphthoxazines and naphthopyrans. Particular preference is given to photo-chromic Reversacol dyes from J. Robinson (Huddersfield, England), e.g. Gray 219, Gray 208, Gray 306, Gray 195, Brown 105, Flamme 29 B, Sea Green 5, Velvet Blue, Sunflower, Graphite and Palatinate Purple.
The amount of these dyes added to the plastics matrix is a function of the layer thickness. A very small thickness requires a high concentration. By way of example, the amounts added of the dyes are from 0.001%
to 0.3% at a thickness of 3 mm. At very small layer : thicknesses, up to 10% of dyes may be added. It has been found that good phototropic properties are detectable when the thickness of the intermediate layer is from 0.01 to 5 mm. The best results were achieved with layer thicknesses of from 0.1 to 3 mm. Mixtures of various dyes may also be used.
It has been found that the inventive sandwich elements can be produced by various processes. A particularly suitable process is the cell casting process. The cell casting process here is used to produce the polymethyl methacrylate sheets separately. The temperature and time for heat-conditioning are set as a function of the thickness of the sheets. The conventional additives, e.g. UV filters, initiators, dyes or stabilizers, may be added. The intermediate layer is then cast with the appropriate additives, e.g. phototropic dyes and, if appropriate, plasticizers, between the polymethyl meth-acrylate sheets. The bond is produced via swelling processes. The PMMA sheets may be treated with cross-linking agents in order to regulate the swelling.
Another suitable process for producing the inventive sandwich elements is the internal coextrusion process.
EP1270176 describes a process for producing multilayer hollow-chamber profiled sheets. This process produces an upper and a lower layer from a plastics melt and a layer situated within the hollow-chamber profile and composed of a plastics melt by coextrusion of the plastics melt and use of an extrusion die, and then calibration of the resultant extrudate. The inventive sandwich elements can be produced by this process using an appropriately designed extrusion die.
The invention therefore also comprises the cell casting process and the internal coextrusion process for producing the inventive sandwich elements.
The polymethyl methacrylate sandwich elements with phototropic dyes are versatile. By way of example, they can be used for automatic shading systems in the construction sector, e.g. greenhouses, conservatories, glazing (e.g. skylights), display windows.
The examples given below are given to provide better illustration of the present invention, but are not intended to restrict the invention to the features disclosed herein.
Examples Example 1 Colourless acrylic sheet for outer panes of the sandwich element The following additives are dissolved, with stirring, in 998 parts of methyl methacrylate prepolymer (viscosity about 1000 cP):
1 part of 2,2'-azobis(2,4-dimethylvaleronitrile) 1 part of glycol dimethacrylate Light stabilizers may also be optionally added in order to protect the photochromic inner layer.
Suitable products for this purpose are HALS products, such as Tinuvin 770, and UV absorbers which are particularly effective in the short-wavelength UV
region, e.g. Sanduvor VSU.
The mixture is vigorously stirred, charged to a silicate glass cell of 400 x 500 mm format with a 3 mm-thickness separating bead, and polymerized in a water bath for 16 h at 45 C. Completion of the polymerization takes place in a heat-conditioning cabinet for 4h at 115 C.
Example 2 Photochromic inner layer of the sandwich element:
The following additives are dissolved, with stirring, in 9988 parts of butyl methacrylate:
5 parts of 2,2'-azobis(isobutyronitrile) 5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) 1 part of Reversacol Sunflower Bt 278/13 (photochromic dye from James Robinson, England) 1 part of Reversacol Palatinate Purple (photochromic dye from James Robinson, England) The mixture is vigorously stirred, charged to a cell composed of colourless acrylic sheet from Experiment 1 with a 3 mm-thickness bead as separator, and poly-merized in a water bath for 22 h at 50 C.
This gives a transparent, slightly yellowish sheet with the high mechanical strength typical of poly-methacrylate. The result of irradiation with sunlight is that, depending on light intensity, the sheet becomes markedly more strongly coloured after from about 30 seconds to 2 minutes, and assumes a grey-brown to brown colour.
Claims (13)
1. Polymethyl methacrylate sandwich elements comprising two polymethyl methacrylate sheets and an intermediate layer which comprises phototropic dyes.
2. Polymethyl methacrylate sandwich elements according to Claim 1, characterized in that the intermediate layer comprises polyacrylates or alkylated polymethacrylates, preferably polybutyl methacrylates.
3. Polymethyl methacrylate sandwich elements according to Claim 2, characterized in that the intermediate layer comprises comonomers.
4. Polymethyl methacrylate sandwich element according to Claims 1 to 3, characterized in that the intermediate layer comprises plasticizers.
5. Polymethyl methacrylate sandwich element according to Claims 1 to 4, characterized in that the inter-mediate layer comprises spironaphthoxazines or naphthopyrans.
6. Polymethyl methacrylate sandwich element according to Claims 1 to 5, characterized in that the thickness of the intermediate layer is from 0.01 to 5 mm, preferably from 0.1 to 3 mm.
7. Polymethyl methacrylate sandwich element according to Claim 6, characterized in that the intermediate lay~r comprises amounts of from 0.001 to 10% of phototropic dyes.
8. Polymethyl methacrylate sandwich element according to Claim 1, characterized in that the polymethyl methacrylate sheets comprise light stabilizers.
9. Polymethyl methacrylate sandwich element according to Claim 1, characterized in that the polymethyl methacrylate sheets comprise dyes.
10. Polymethyl methacrylate sandwich element according to Claim 1, characterized in that the polymethyl methacrylate sheets comprise comonomers, in particular crosslinking agents.
11. Process for production of polymethyl methacrylate sandwich elements according to Claim 1, characterized in that, in the cell casting process, an intermediate layer is cast between two polymethacrylate sheets and the materials are bonded to one another by way of a heat-conditioning process.
12. Process for production of polymethyl methacrylate sandwich elements according to Claim 1, characterized in that internal coextrusion is used to produce two polymethacrylate sheets with an intermediate layer.
13. Use of polymethyl methacrylate sandwich elements in the construction sector.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004053817.4 | 2004-11-04 | ||
DE102004053817A DE102004053817A1 (en) | 2004-11-04 | 2004-11-04 | Acrylic glass with photochromic properties |
PCT/EP2005/010556 WO2006048089A1 (en) | 2004-11-04 | 2005-09-30 | Acrylic glass having photochromic properties |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2580765A1 true CA2580765A1 (en) | 2006-05-11 |
Family
ID=35432736
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002580765A Abandoned CA2580765A1 (en) | 2004-11-04 | 2005-09-30 | Acrylic glass having photochromic properties |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1807261A1 (en) |
JP (1) | JP2008518809A (en) |
KR (1) | KR20070074597A (en) |
CN (1) | CN101022950A (en) |
AU (1) | AU2005300858A1 (en) |
BR (1) | BRPI0517270A (en) |
CA (1) | CA2580765A1 (en) |
DE (1) | DE102004053817A1 (en) |
WO (1) | WO2006048089A1 (en) |
ZA (1) | ZA200703580B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7704586B2 (en) | 2005-03-09 | 2010-04-27 | Degussa Ag | Plastic molded bodies having two-dimensional and three-dimensional image structures produced through laser subsurface engraving |
DE102007021199B4 (en) | 2006-07-17 | 2016-02-11 | Evonik Degussa Gmbh | Compositions of organic polymer as matrix and inorganic particles as filler, process for their preparation and their use and moldings produced therewith |
CN103481564B (en) * | 2013-08-16 | 2016-04-13 | 武汉羿阳科技有限公司 | A kind of fenestrated membrane of automatic adjustment light transmittance |
CN110818936B (en) * | 2019-11-14 | 2022-04-05 | 陕西理工大学 | Organic glass and preparation method and application thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE7316334U (en) * | 1973-04-30 | 1973-08-23 | Jenaer Glaswerk Schott & Gen | TRANSLUCENT PHOTOTROPIC COMPOSITE BODY |
JPS6424740A (en) * | 1987-07-20 | 1989-01-26 | Toyota Motor Corp | Light-shield glass for windshield of automobile |
JP3404759B2 (en) * | 1992-01-10 | 2003-05-12 | 橋本フォーミング工業株式会社 | Scattered light lighting window and manufacturing method |
JPH06138577A (en) * | 1992-09-08 | 1994-05-20 | Mitsubishi Kasei Corp | Photochromic laminate |
US6084702A (en) * | 1998-10-15 | 2000-07-04 | Pleotint, L.L.C. | Thermochromic devices |
TW534869B (en) * | 2000-06-09 | 2003-06-01 | Mitsubishi Gas Chemical Co | Synthetic resin laminate having both polarization characteristic and photochromism characteristic, and molded article obtained therefrom |
US6547390B1 (en) * | 2000-09-11 | 2003-04-15 | Exxene Corporation | Top stabilized photochromic lens system |
DE10129702A1 (en) * | 2001-06-22 | 2003-01-02 | Roehm Gmbh | Extrusion tool for the production of hollow profile sheets made of thermoplastic material with internal coextruded layer |
US20040131872A1 (en) * | 2001-11-29 | 2004-07-08 | Shaobin Fan | Photochromic articles and methods for making them |
-
2004
- 2004-11-04 DE DE102004053817A patent/DE102004053817A1/en not_active Withdrawn
-
2005
- 2005-09-30 JP JP2007539479A patent/JP2008518809A/en active Pending
- 2005-09-30 WO PCT/EP2005/010556 patent/WO2006048089A1/en active Application Filing
- 2005-09-30 AU AU2005300858A patent/AU2005300858A1/en not_active Abandoned
- 2005-09-30 EP EP05791361A patent/EP1807261A1/en not_active Withdrawn
- 2005-09-30 KR KR1020077010075A patent/KR20070074597A/en not_active Application Discontinuation
- 2005-09-30 CA CA002580765A patent/CA2580765A1/en not_active Abandoned
- 2005-09-30 CN CNA2005800314417A patent/CN101022950A/en active Pending
- 2005-09-30 BR BRPI0517270-5A patent/BRPI0517270A/en not_active Application Discontinuation
-
2007
- 2007-05-03 ZA ZA200703580A patent/ZA200703580B/en unknown
Also Published As
Publication number | Publication date |
---|---|
JP2008518809A (en) | 2008-06-05 |
ZA200703580B (en) | 2008-08-27 |
WO2006048089A1 (en) | 2006-05-11 |
CN101022950A (en) | 2007-08-22 |
DE102004053817A1 (en) | 2006-05-11 |
KR20070074597A (en) | 2007-07-12 |
EP1807261A1 (en) | 2007-07-18 |
BRPI0517270A (en) | 2008-10-07 |
AU2005300858A1 (en) | 2006-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
RU2453563C2 (en) | Polymethylmethacrylate film having particularly high weather resistance and highly efficient protection from ultraviolet radiation | |
JPS58138885A (en) | Different shape material | |
CN101730717A (en) | Pmma/pvdf film with particularly high weathering stability and high uv protective action | |
ES2241355T3 (en) | PROCEDURE FOR MANUFACTURING PVDF SHEETS AND POLYACRYLATES. | |
US8323535B2 (en) | Photochromic compositions and photochromic films | |
KR20160140751A (en) | color changing material | |
DE10243062A1 (en) | A sanitary material made from thermoplastic polymethyl methacrylate molding material useful for sanitary material resistant to hot water,which is crack resistant, cheap to produce, and can be recycled | |
KR20100054758A (en) | Laminate | |
EP1362077B1 (en) | Photochromic plastic object | |
CA2580765A1 (en) | Acrylic glass having photochromic properties | |
KR20070001043A (en) | Composition coextrudable with pvdf and having no stress-whitening effect | |
JPWO2017217429A1 (en) | Black film | |
KR100428639B1 (en) | Multi-layered transparent sheet for exterior | |
US20060019092A1 (en) | Method of forming a breathable film cover | |
IL43267A (en) | Extruded sections of synthetic thermoplastic materials | |
CN1054803C (en) | Polycarbonic acid ester resin layered products absorbing near-infrared and formed products made of same | |
US20090250670A1 (en) | Photochromic films and method for manufacturing the same | |
JP7278810B2 (en) | Acrylic resin film and its manufacturing method | |
JP2004338222A (en) | Acrylic resin film improved in durability of fluorescence | |
EP0736645B1 (en) | Wall elements | |
KR101712416B1 (en) | Composite sheet having excellent weather-ability | |
KR20230134329A (en) | Uv protective acrylic laminate films and manufacturing method thereof | |
KR20040057054A (en) | Composite material and Waterproof sheet be utilized Adhesion film Scrap for making of Safety glass and Method for forming the same | |
JPH04202032A (en) | Intermediate film for laminated glass | |
DE102007002553A1 (en) | Photochromic material comprises a photochromic layer formed by three-dimensional radical polymerization between two polycarbonate layers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |