WO2002018133A2 - Low emissivity article with low-e fluoropolymer layer - Google Patents
Low emissivity article with low-e fluoropolymer layer Download PDFInfo
- Publication number
- WO2002018133A2 WO2002018133A2 PCT/US2001/024862 US0124862W WO0218133A2 WO 2002018133 A2 WO2002018133 A2 WO 2002018133A2 US 0124862 W US0124862 W US 0124862W WO 0218133 A2 WO0218133 A2 WO 0218133A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- low
- coating
- layer
- fluoropolymer
- absorbing particles
- Prior art date
Links
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 39
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 claims abstract description 84
- 239000011248 coating agent Substances 0.000 claims abstract description 77
- 239000002245 particle Substances 0.000 claims abstract description 53
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 52
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 239000003365 glass fiber Substances 0.000 claims description 13
- 239000002923 metal particle Substances 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 11
- 239000008199 coating composition Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 description 45
- 239000004810 polytetrafluoroethylene Substances 0.000 description 34
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 34
- 239000012528 membrane Substances 0.000 description 25
- 230000005855 radiation Effects 0.000 description 22
- 230000005540 biological transmission Effects 0.000 description 15
- -1 polytetrafluoroethylene Polymers 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- 239000004753 textile Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 239000004446 fluoropolymer coating Substances 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005670 electromagnetic radiation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 1
- OADAUSIWVYYLON-UHFFFAOYSA-N 4-propoxypent-1-enyl hypofluorite Chemical compound C(CC)OC(CC=COF)C OADAUSIWVYYLON-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RMGXRTOOBAULEX-UHFFFAOYSA-N FC(=C(C(C(OC(C(F)(F)F)(F)F)(F)F)(F)F)F)OC(=C(F)C(C(F)(F)OC(C(F)(F)F)(F)F)(F)F)F Chemical compound FC(=C(C(C(OC(C(F)(F)F)(F)F)(F)F)(F)F)F)OC(=C(F)C(C(F)(F)OC(C(F)(F)F)(F)F)(F)F)F RMGXRTOOBAULEX-UHFFFAOYSA-N 0.000 description 1
- GHSBRBCKXUSPAS-UHFFFAOYSA-N FC(=C(C(C(OC(F)(F)F)(F)F)(F)F)F)OC(=C(F)C(C(F)(F)OC(F)(F)F)(F)F)F Chemical compound FC(=C(C(C(OC(F)(F)F)(F)F)(F)F)F)OC(=C(F)C(C(F)(F)OC(F)(F)F)(F)F)F GHSBRBCKXUSPAS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- XBSVWZGULSYIEG-UHFFFAOYSA-N ethenyl hypofluorite Chemical class FOC=C XBSVWZGULSYIEG-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical group C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- FOKCKXCUQFKNLD-UHFFFAOYSA-N pent-1-enyl hypofluorite Chemical compound C(CC)C=COF FOKCKXCUQFKNLD-UHFFFAOYSA-N 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04H—BUILDINGS OR LIKE STRUCTURES FOR PARTICULAR PURPOSES; SWIMMING OR SPLASH BATHS OR POOLS; MASTS; FENCING; TENTS OR CANOPIES, IN GENERAL
- E04H15/00—Tents or canopies, in general
- E04H15/32—Parts, components, construction details, accessories, interior equipment, specially adapted for tents, e.g. guy-line equipment, skirts, thresholds
- E04H15/54—Covers of tents or canopies
-
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/12—Roof covering by making use of flexible material, e.g. supplied in roll form specially modified, e.g. perforated, with granulated surface, with attached pads
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D7/00—Roof covering exclusively consisting of sealing masses applied in situ; Gravelling of flat roofs
- E04D7/005—Roof covering exclusively consisting of sealing masses applied in situ; Gravelling of flat roofs characterised by loose or embedded gravel or granules as an outer protection of the roof covering
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
Definitions
- the present invention relates to technical membranes that comprise a low emissivity layer (low- e layer) comprising a fluoropolymer having dispersed therein infrared absorbing particles.
- the present invention further relates to a roof, wall or tent that comprises a low-e layer.
- Such membranes typically comprise a glass fiber or polyester fiber web, e.g. glass fiber textile, that is coated with polyvinyl chloride, polytetrafluoroethylene or silicone resin.
- Such membranes can be used for example as roofs to cover large areas such as in football stadiums and airport halls.
- the membranes are especially suitable for this purpose due to their low weight making it possible to make lightweight roof constructions.
- the Puchheim city hall with its multilayer roof skin was made primarily of noncombustible lightweight membrane materials and was honored with the third awarding of the international prize for textile architecture at TechTextil 1999. Thermal insulation was implemented by means of sand integrated between several layers.
- the Kunststoff Airport Center (MAC) West with its forum roof made of a combination of a glass fiber membrane coated with polytetrafluoroethylene (PTFE), and a multilayer safety glass was awarded a prize.
- MAC Munich Airport Center
- these membranes also have the property of repelling dirt and they have a high resistance to rotting.
- these membranes are light transmitting, i.e. translucent and are fire proof.
- Noncombustible materials have been disclosed in DE A 23 15 259, which describes a textile that is coated with a glass bead tetrafluoroethylene polymer mixture and which is not combustible. However, this textile does not have a climatizing effect.
- an adhesive layer preferably made of silicone rubber, latex milk, or a phthalate resin adhesive is applied to a glass fiber fabric, whereupon glass beads are pressed into the adhesive layer.
- This material is intended to provide high mechanical tensile and tear strength, high light reflection, satisfactory thermal insulation and light transmission, a high degree of resistance to fire, resistance to wear, weathering, contamination and insect pests, and an extremely pleasing aesthetic effect.
- thermal insulation and fire resistance there is an interest in improving these properties, particularly the thermal insulation and fire resistance.
- technical membranes can reduce the heat transport between the outside and an interior space. Heat can be transported by several ways between a warm and a cool place. Such ways include convection, heat conduction as well as transport of heat through radiation.
- Heat transport through radiation involves a body at a higher temperature radiating electromagnetic radiation against a body at a lower temperature.
- the intensity of this radiation depends on the temperature difference between the two bodies.
- the emitted power or emittance is given by the following formula:
- W ⁇ ⁇ T 4
- W represents the emittance
- ⁇ represents the emissivity
- ⁇ is the Stephan-Boltzman constant.
- the emissivity is a value between 0 and 1 and is the ratio of the radiation emitted by a surface to the radiation emitted by a perfect black body at the same temperature.
- This type of heat transport can amount to 90% of the total heat transport.
- the radiation in the infrared part of the spectrum will contribute to heating and is moreover experienced as unpleasant by human beings.
- a reduced level of infrared radiation will provide more comfort.
- a higher ambient temperature can be tolerated if the level of infrared radiation is reduced or minimized. Accordingly, by reducing the infrared emission, one can allow a higher temperature for a room, thereby saving costs in cooling the room.
- EP 1 053 867 discloses a technical membrane that comprises a glass fiber web that has been coated with a modified PTFE on which there is provided a so-called low-e coating.
- EP 1053867 does not give much detail as to the composition of this low-e coating, it appears that this low-e coating is applied through vacuum deposition. This has the disadvantage however that the low-e coating is prone to being damaged when constructing for example a roof therewith or while cleaning and moreover is prone to corrosion. Accordingly, it is taught to use a protective coating on the low-e coating. Unfortunately, this reduces the effectiveness of the low-e coating.
- WO 99/39060 similarly teaches a technical membrane that comprises a low-e coating. No details are given as to the composition of this low-e coating.
- WO 99/39060 teaches to arrange the technical membrane on a sound barrier layer so as to additionally provide for sound insulation.
- WO 99/39060 also teaches the desire to protect the low-e coating with a protective layer against abra
- Metallized coatings for textiles have also been used in for example EP 927 328 as electromagnetic camouflage materials.
- JP 05-318659 teaches coating a glass fiber textile with a fluoropolymer coating that contains aluminum particles in order to provide for liquid and gas barrier properties and additionally reflection of heat or light.
- US 3,709,721 teaches polytetrafluoroethylene (PTFE) coatings that comprise a hard particulate filler such as for example aluminum to provide a heat and abrasion resistant material.
- PTFE polytetrafluoroethylene
- WO 96/05360 teaches a multi-layer textile composite that has layer of fluoropolymer having aluminum particles arranged as an inner layer. The textile composite is taught for use in conveyor belts that are used at elevated temperature in for example commercial food cooking processes.
- none of these teachings have appreciated the low emissivity properties that may be obtained with a fluoropolymer layer containing metal particles.
- the present inventors have thus determined it desirable to find an improved low-e layer that can be used in a technical membrane to effectively reduce emission of electromagnetic radiation, in particular of infrared radiation. It would furthermore be desirable that such low-e coating has a good abrasion resistance and does not require the use of a protective layer. It would be furthermore desirable to find low emittance materials that are difficult to burn, i.e. materials that can be classified according to DIN 4102 as hardly flammable or non-flammable material. According to one of the requirements in order to be classified according to DIN 4102 as non- flammable or hardly flammable material, the material should have a caloric value of less than 4200 J/g as measured according to DIN 51900.
- a layer of fluoropolymer having dispersed therein infrared absorbing (IR-absorbing) particles can be used as a low-e layer, i.e. such a layer has a low emissivity (0.6 or less, preferably 0.5 or less, more preferably 0.4 or less) and can be used to reduce the amount of heating or cooling that is required to maintain an interior space at a desired temperature.
- interior space is meant a space enclosed by a roof and/or walls such as for example a room or hall in a building.
- the low-e layer can be used as a barrier layer for infrared radiation and can be used to reduce the amount of infrared radiation in a room.
- the low-e layer is arranged as the outermost layer of a low emittance article, e.g. a technical membrane, so as to achieve an emissivity of not more than 0.6 for the low emittance article.
- a low emittance article e.g. a technical membrane
- the present invention provides a low emittance article comprising a substrate having on at least one major surface thereof at least two layers, the outermost layer of which comprises a fluoropolymer and IR-absorbing particles in the form of flakes distributed in the outermost layer.
- the IR-absorbing particles typically have an average particle size of less than 25 ⁇ m, typically less than 15 ⁇ m, preferably less than 3 ⁇ m, more preferably not more than 0.8 ⁇ m.
- the IR-absorbing particles are preferably distributed in the outermost layer in an amount of at least 10%, more preferably at least 16% by weight.
- the term "average particle size" indicates the average along the largest dimension of the particles.
- the present invention provides a coating composition for producing a low emissivity coating, the composition comprising a dispersion of a fluoropolymer and metal particles in the form offtakes.
- the invention in one of its aspects also provides a roof, wall or tent that comprises a low emissivity layer of a fluoropolymer having dispersed therein infrared absorbing particles.
- the present invention has recognized that a coating of fluoropolymer having dispersed therein IR absorbing particles, can effectively be used as a low emissivity coating, i.e., a layer that provides a barrier against heat transport through radiation, in particular infrared radiation.
- the low-e coating has a high scratch and abrasion resistance.
- articles including the low-e coating such as technical membranes are easy to transport and handle and can be manufactured in a convenient and cost effective way.
- the low-e coating in accordance with this invention typically has an emissivity of not more than 0.6, preferably more than 0.5, more preferably not more than 0.4.
- the low-e coating typically emits IR radiation only slowly.
- the low-e coating when arranged towards the innerspace of a room, the low-e coating will emit less IR radiation to the room and thereby help cooling the room. Additionally, during the night when the room may cool too much, the low emissivity of the low-e coating will help protect the room against cooling.
- the low-e coating contains a fluoropolymer.
- Suitable fluoropolymers for use in the low-e coating are typically fluoropolymers that have a fluorinated carbon backbone.
- the fluoropolymer backbone is at least 50% by weight fluorinated.
- the partially fluorinated backbone of the fluoropolymer may in addition to fluorine contain hydrogen or chlorine.
- the fluoropolymer for use in the low-e coating may also include perfluoropolymers, i.e., polymers that have a fully fluorinated or perfluorinated backbone.
- PTFE polytetrafluoroethylene
- polymers comprising one or more units derived from vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, hexafluoropropylene
- fluorinated vinyl ethers including perfluoro vinyl ethers such as perfluor
- Fluoropolymers for use in the low-e coating further include for example in addition to PTFE, PTFE modified with for example hexafluoropropylene or a perfluorovinyl ether and thermoplastic melt-processable fluoropolymers such as copolymers of tetrafluoroethylene and hexafluoropropylene and/or one or more perfluorovinyl ethers. It will further be clear to one skilled in the art that mixtures of fluoropolymers may be used as well such as for example mixtures of PTFE and thermoplastic melt-processable fluoropolymers.
- the infrared absorbing particles for use in the low-e coating are preferably metal particles including particles that have been provided with a metal coating on their surface such as for example glass microspheres having been metallized at their surface.
- the metal particles may be oxidized at their surface.
- Metal particles are capable of absorbing IR radiation and have a low emissivity.
- suitable metal particles include noble metals such as silver or gold as well as other metals such as aluminum, copper, zinc and combinations thereof, including alloys of such metals.
- the average particle size of the IR absorbing particles is typically less than 25 ⁇ m, preferably less than 3 ⁇ m, more preferably in the order of colloidal particles, i.e., not more than 800 nm. By using smaller particles, the light transmission of the coating can be optimized while maintaining a low emissivity.
- the geometry of the particles can be spherical or substantially spherical such as elliptical.
- the particles are in the form of flakes preferably having an average particle size, measured along the largest dimension, of not more than 25 ⁇ m, preferably not more than 20 ⁇ m, and preferably having an average thickness of between 0.01 ⁇ m and 1 ⁇ m, preferably between 0.05 ⁇ m and 0.5 ⁇ m.
- IR-absorbing particles in the form of flakes may provide the advantage that they are capable of orientation during coating such that even at low amounts of the particles, an effective low emissivity can be obtained.
- the amount of the IR-absorbing particles is typically at least about 2% by weight based on the total weight of solids, preferably at least 5-6% by weight, more preferably at least 10% by weight and most preferably at least about 15-16% by weight.
- a typical range of the amount of IR-absorbing particles is between 2% by weight and 70% by weight, preferably between 10 and 50% by weight.
- the thickness of the low-e layer is preferably kept minimal to provide for a higher light transmission.
- the thickness of the low-e layer will be not more than 0.3 mm, preferably not more than 0.05 mm.
- the low-e coating may contain additional ingredients such as non-flammable fillers such as glass spheres, mica pigments, ceramics or titanium dioxide. Such fillers may for example be included in the low-e coating in an amount of 2 to 80% by weight.
- the low-e coating can be used to provide a low emittance material, in particular to provide a technical membrane, e.g., a light translucent membrane.
- the low emittance material comprising the low-e coating will typically have a emissivity of not more than 0.6, preferably not more than 0.5 and more preferably not more than 0.4.
- the desired emissivity can be selected by one skilled in the art through routine experimentation and will generally depend on such factors as the thickness of the low-e coating, the position of the low-e coating in the layer package of the low emittance material, the amount of IR absorbing particles in the low-e coating and the size and geometry of the IR absorbing particles.
- the low-e coating is preferably provided as close as possible to the surface of the low emittance material, most preferably as an outermost layer.
- Light transmission of the material can be increased by bleaching processes such as annealing and UV radiation.
- the low emittance material will preferably have a light transmission of at least 0.5%, preferably at least 0.8%, more preferably at least 1%. With the low emittance material of the present invention, even a light transmission of 2% or more, e.g., 9% or more can be achieved. It should be noted here that a light transmission of at least 2% may already provide a sufficient amount of supporting light in a room.
- the low emittance material comprises a substrate, for example a flat substrate provided with the low-e coating.
- the substrate has a high temperature resistance to allow for the use of high temperatures to provide coatings to the substrate.
- suitable substrates include glass fiber webs or fabrics, e.g. glass fiber cloth which are UV-resistant, organic materials such as polyparaphenylene terephthalamide which is commercially available under the brand KEVLAR, metal fiber fabrics, mineral fiber materials such as felts and mats of glass wool and rock wool.
- the fabric substrates may be woven or non- woven.
- the low emittance material comprises at least two layers on the substrate, the outermost layer of which is the low-e coating.
- the one or more further layers of a multi- layer low emittance material may comprises further layers of fluoropolymer, in particular of polytetrafluoroethylene. Such further layers will generally not comprise the IR absorbing particles of the low-e coating. Such one or more further layers may for example be provided to increase the adhesion of the low-e coating to the substrate of the low emittance material.
- the one or more further layers may contain additional ingredients such as non-flammable fillers such as glass spheres, mica pigments, ceramics or titanium dioxide. Such fillers may for example be included in a further layer in an amount of 2 to 80% by weight.
- a low emittance material may be provided as a translucent technical membrane with the low-e coating as an outermost layer arranged towards the interior of a room. Because of the low emissivity level and adsorption of infrared radiation, the interior will be cooled and moreover, because of the reduced infrared radiation in the room, the climate therein will feel more comfortable. Further, at times when the exterior temperature drops, infrared emission from the low emittance material contributes to protecting the room against cooling.
- the low emittance material may act as a heat accumulator that may be charged by solar radiation during the day and which slowly releases the accumulated energy during the night. Accordingly, the low emittance materials are particularly suitable for use in areas that have a hot climate such as tropical and desert climates.
- the low emittance material may be obtained by coating a substrate, for example glass fiber fabric, with a coating composition comprising the fluoropolymer and the IR-absorbing particles.
- a coating composition comprising the fluoropolymer and the IR-absorbing particles.
- an aqueous dispersion of the fluoropolymer and IR-absorbing particles will be used as the coating composition.
- the coating composition may contain multimodal particle distributions of the fluoropolymer as taught in DE 197 26 802 to provide for dense coatings and a smooth surface.
- a preferred coating composition may contain the IR absorbing particles, for example metal particles such as aluminum in an amount of at least 10% by weight.
- the low-e coating composition may be applied for example through dip coating.
- the substrate may first be coated with one or more fluoropolymer layers, e.g., polytetrafluoroethylene, which do not contain IR absorbing particles.
- fluoropolymer layers e.g., polytetrafluoroethylene
- Suitable glass fiber coating methods are disclosed in for example DE 23 15 259 and US 2 731 068, which are modified such that preferably the last coating is a coating composition used to provide the low-e layer.
- the low emittance material typically will have a caloric value according to DIN 51 900) of not more than 6000 J/g, preferably less than 4200 J/g. Accordingly, the low emittance material will be hardly flammable.
- the low-e coating may be used in roofs, wall or tents.
- roofs, wall or tents have been disclosed in EP 1 053 867 and WO 99/39060.
- roofs, wall or tents comprise a translucent technical membrane comprising a substrate, for example as disclosed above that is provided on at least one side with a fluoropolymer coating, e.g., polytetrafluoroethylene, and a low-e coating, preferably as an outermost layer.
- the low-e coating is typically arranged towards the inner side of a room thereby reducing the amount of energy needed to cool the room.
- the low-e coating When the low-e coating is arranged towards the exterior, the low-e coating will inhibit loss of heat through emission towards the outside and thus reduces the amount of heating that is required. By providing the low-e coating on both sides, an improved heat insulation results.
- a translucent technical membrane having the Iow-e coating may further be combined with other layers such as for example sound barrier layers as disclosed in for example WO 99/39060 which is incorporated herein by reference.
- a light transmitting sound barrier layer is arranged at a distance to the outer layer of the technical membrane that contains a low-e coating.
- the substrate of the technical membrane e.g., glass fiber fabric, preferably has openings in it such that sound and light can pass through the technical membrane to the light transmitting sound barrier.
- the low-e coating may also be used in other materials that are typically used to cover a room against penetration of sun rays.
- Such materials include in particular shading materials including movable shading materials such as blinds, awnings, roll-down shutters, curtains, ashamedies and lamella.
- shading materials may be used on their own to mitigate temperature conditioning of a room or they can be used in combination with a roof or wall having the low-e coating.
- the emissivity of the materials in the following examples was measured using an Emissionmeter Model AE from Devices and Services Co., Dallas, Texas, USA according to the procedures laid out by the manufacturer of the machine.
- the emissionmeter was equipped with a differential thermopile as a radiation detector.
- the radiation detector was heated to 82°C and has a nearly constant response to the thermal wavelengths (3 to 30 ⁇ m).
- the device was first calibrated using a standard having high emissivity (0.93) and a standard having a low emissivity (0.04).
- the unknown sample was thereafter measured against the standard having a high emissivity.
- PTFE polytetrafluoroethylene
- FEP copolymer of tetrafluoroethylene and hexafluoropropylene commercially available as
- PFA copolymer of tetrafluoroethylene and perfluoro-(n-propyl vinyl) ether commercially available as DyneonTM PFA 6900 N.
- a glass cloth in linen weave having a weight per unit area of 442 g/m 2 was coated on both sides with 659 g/m 2 of coating material in four coats.
- the first coating was applied using a 50% by weight dispersion of PTFE (diluted from commercially available PTFE dispersion DyneonTM TFX 5060), the second and third coats were made using a 62% by weight PTFE dispersion containing glass microspheres and commercially available as DyneonTM TFX 5041.
- a fourth coating was applied at 50 g/m 2 of PTFE using a dispersion containing 60% by weight of PTFE (commercially available as DyneonTM TFX 5060).
- This glass fiber cloth containing only PTFE coatings without IR absorbing particles has an emissivity of 0.88.
- the coating procedure as carried out in the comparative example was repeated, but in place of the last coat of DyneonTM TFX 5060 there was applied, a PTFE dispersion (diluted from commercially available PTFE dispersion DyneonTM TFX 5060) having containing 10% by weight of aluminum paste relative to the weight of PTFE solids and having a total amount of solids of 62% by weight.
- the aluminum paste comprised 65% by weight of aluminum flakes, having an average size of 13 ⁇ m and a thickness of 0.2 ⁇ m, in water.
- the aluminum containing coating was applied such at an amount of 42.5g/m 2 which contained about 5.9% of aluminum.
- the emissivity of the coated material was 0.60 and the light transmission was 0.1%.
- Example 2 Example 2
- the coating procedure as carried out in the comparative example was repeated to coat a total weight of coating material of 656g/m 2 , but in place of the last coat of DyneonTM TFX 5060 there was applied, a PTFE dispersion (diluted from commercially available PTFE dispersion DyneonTM TFX 5060) having containing 30% by weight of aluminum paste used in example 1 relative to the weight of solids and having a total amount of solids of 52% by weight.
- the aluminum containing coating was applied such at an amount of 22g/m 2 which contained about 18.2%) of aluminum.
- the emissivity of the coated material was 0.50 and the light transmission was 0.4%.
- Example 2 The material per Example 2 was annealed for 12 hours at 250°C. The transmission thereby increased to 1%. The emissivity was unchanged at 0.5.
- the coating procedure as carried out in the comparative example was repeated to coat a total weight of coating material of 663g/m 2 , but in place of the last coat of DyneonTM TFX 5060 there was applied, a PTFE dispersion (diluted from commercially available PTFE dispersion DyneonTM TFX 5060) having containing 30% by weight of aluminum paste of Example 1 relative to the weight of solids and having a total amount of solids of 42% by weight.
- the aluminum containing coating was applied such at an amount of 30g/m 2 which contained about 16.1% of aluminum.
- the emissivity of the coated material was 0.50 and the light transmission was 1%.
- the caloric value of the low emittance material as measured according to DIN 51900 part 1 was the caloric value of the low emittance material as measured according to DIN 51900 part 1 was the caloric value of the low emittance material as measured according to DIN 51900 part 1 was the caloric value of the low emittance material as measured according to DIN 51900 part 1 was the caloric value of the low emittance material as measured according to DIN 51900 part 1 was the caloric value of the low emittance material as measured according to DIN 51900 part 1 was
- Example 4 The material per Example 4 was annealed for 12 hours at 280°C. The transmission increased to 1.1%. The emissivity was unchanged at 0.5.
- Example 4 The procedure of Example 4 was repeated but instead of the aluminum containing PTFE dispersion, a fluoropolymer dispersion containing a mixture of PTFE and a PFA in equal amounts was used.
- This fluoropolymer dispersion further contained 50% by weight of the aluminum paste of Example 1 containing 65% by weight of aluminum in water.
- the total amount of solids in the dispersion was 65% by weight and 54 g/m 2 (dry weight) of this coating was applied on one side of the low emittance material as a last coating.
- the amount of aluminum in this coating was about 33% by weight.
- the emissivity was 0.45, the light transmission 0.7% and the caloric value according to DIN 51900 was 4015 J/g.
- Example 7 The procedure of Example 4 was repeated but instead of the aluminum containing PTFE dispersion, a fluoropolymer dispersion containing a mixture of PTFE and FEP in equal amounts was used. This fluoropolymer dispersion further contained 100% by weight of the aluminum paste containing 65% by weight of aluminum in water. The total amount of solids in the dispersion was 30% by weight and 12 g/m 2 (dry weight) of this coating was applied on one side of the low emittance material as a last coating. The amount of aluminum in this coating was about 40% by weight based on solids. The emissivity was 0.33 and the light transmission 0.7%.
- a glass cloth in linen weave having a weight per unit area of 100 g/m 2 was coated with 44.9 g/m 2 of coating material in three coatings using DyneonTM TFX 5060.
- DyneonTM TFX 5060 As a last coat on one side there was applied 1.1 g/m 2 (dry weight) of a dispersion containing a total solids of 20% by weight and containing PTFE and FEP in equal amounts and the aluminum paste of Example 1 containing 65% by weight of aluminum in water.
- the amount of aluminum in the dispersion was about 40% by weight based on solids.
- the light transmission was 9% and the emissivity 0.45.
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Acoustics & Sound (AREA)
- Electromagnetism (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tents Or Canopies (AREA)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001279236A AU2001279236A1 (en) | 2000-08-29 | 2001-08-08 | Low emissivity article with low-e fluoropolymer layer |
JP2002523083A JP2004507386A (ja) | 2000-08-29 | 2001-08-08 | 低輻射率フルオロポリマー層を有する低輻射率物品 |
EP01957498A EP1313923A2 (en) | 2000-08-29 | 2001-08-08 | Low emissivity article with low-e fluoropolymer layer |
US10/333,440 US20040013868A1 (en) | 2000-08-29 | 2001-08-08 | Low emissivity article with low-e-fluoropolymer layer |
CA002418005A CA2418005A1 (en) | 2000-08-29 | 2001-08-08 | Low emissivity article with low-e fluoropolymer layer |
US11/050,364 US20050129845A1 (en) | 2001-08-08 | 2005-02-03 | Process for maintaining a desired temperature |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10042464.3 | 2000-08-29 | ||
DE2000142464 DE10042464A1 (de) | 2000-08-29 | 2000-08-29 | Wärmeabsorbierende Membranen |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/050,364 Division US20050129845A1 (en) | 2001-08-08 | 2005-02-03 | Process for maintaining a desired temperature |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002018133A2 true WO2002018133A2 (en) | 2002-03-07 |
WO2002018133A3 WO2002018133A3 (en) | 2002-04-18 |
Family
ID=7654221
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/024862 WO2002018133A2 (en) | 2000-08-29 | 2001-08-08 | Low emissivity article with low-e fluoropolymer layer |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1313923A2 (ja) |
JP (1) | JP2004507386A (ja) |
AU (1) | AU2001279236A1 (ja) |
CA (1) | CA2418005A1 (ja) |
DE (1) | DE10042464A1 (ja) |
WO (1) | WO2002018133A2 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2096225A1 (en) * | 2008-02-28 | 2009-09-02 | Flag S.p.A | Synthetic waterproofing covering, particularly for roofs, and method for manufacturing |
EP2108626A1 (fr) * | 2008-04-11 | 2009-10-14 | Electricité de France | Produit d'isolation thermique a base de laine minerale et de poudre metallique a faible emissivite |
WO2010048187A1 (en) * | 2008-10-20 | 2010-04-29 | Basf Corporation | Roofing materials with metallic appearance |
WO2008151603A3 (de) * | 2007-06-11 | 2013-07-11 | ROWO Coating Gesellschaft für Beschichtung mbH | Transparentes flächenmaterial für architektonische zwecke |
WO2015114253A1 (fr) * | 2014-01-31 | 2015-08-06 | Decathlon | Dispositif de protection solaire |
EP2203610B1 (fr) * | 2007-10-26 | 2017-11-08 | Electricité de France | Materiau thermoisolant a base de fibres organiques et d'une poudre rupteur de rayonnement infrarouge, et son utilisation en isolation thermique |
US20180311943A1 (en) * | 2015-10-28 | 2018-11-01 | Madico, Inc. | Multilayer composite films for architectural applications |
US20190308142A1 (en) * | 2016-08-26 | 2019-10-10 | Taiyo Kogyo Corporation | Fluororesin film material and production process therefor |
US10751973B2 (en) | 2016-03-21 | 2020-08-25 | Saint-Gobain Performance Plastics Corporation | Architectural membrane |
CN112601661A (zh) * | 2018-08-23 | 2021-04-02 | 美国西幔公司 | 具有透光性和拉伸性的多层复合材料 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2842556B1 (fr) * | 2002-07-17 | 2009-01-30 | Abeil | Sous tente composite isotherme pour environnements extremes et materiaux correspondants |
DE102007045783B4 (de) * | 2007-09-25 | 2014-10-16 | Joachim Karthäuser | Verfahren zur Herstellung einer elastischen mikroporösen Membran, Membran hergestellt nach dem Verfahren und deren Verwendung |
JP5570306B2 (ja) * | 2010-06-03 | 2014-08-13 | 富士フイルム株式会社 | 熱線遮蔽材 |
JP6466077B2 (ja) * | 2013-04-04 | 2019-02-06 | 日鉄住金鋼板株式会社 | 塗装金属板 |
JP7431105B2 (ja) * | 2020-05-28 | 2024-02-14 | 株式会社日立産機システム | 圧縮機 |
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2000
- 2000-08-29 DE DE2000142464 patent/DE10042464A1/de not_active Ceased
-
2001
- 2001-08-08 AU AU2001279236A patent/AU2001279236A1/en not_active Abandoned
- 2001-08-08 CA CA002418005A patent/CA2418005A1/en not_active Abandoned
- 2001-08-08 JP JP2002523083A patent/JP2004507386A/ja active Pending
- 2001-08-08 EP EP01957498A patent/EP1313923A2/en not_active Withdrawn
- 2001-08-08 WO PCT/US2001/024862 patent/WO2002018133A2/en not_active Application Discontinuation
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US2731068A (en) | 1950-09-23 | 1956-01-17 | Du Pont | Tetrafluoroethylene polymer bonded heat-resistant fabric |
US3709721A (en) | 1970-09-14 | 1973-01-09 | Pennwalt Corp | Heat and abrasion resistant textiles |
DE2315259A1 (de) | 1972-03-27 | 1973-10-11 | Pennwalt Corp | Mit einer glasperlen-tetrafluoraethylenpolymeren-mischung beschichtetes gewebe |
JPH05318659A (ja) | 1992-05-18 | 1993-12-03 | Chuko Kasei Kogyo Kk | 弗素樹脂被覆複合体 |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008151603A3 (de) * | 2007-06-11 | 2013-07-11 | ROWO Coating Gesellschaft für Beschichtung mbH | Transparentes flächenmaterial für architektonische zwecke |
EP2203610B1 (fr) * | 2007-10-26 | 2017-11-08 | Electricité de France | Materiau thermoisolant a base de fibres organiques et d'une poudre rupteur de rayonnement infrarouge, et son utilisation en isolation thermique |
EP2096225A1 (en) * | 2008-02-28 | 2009-09-02 | Flag S.p.A | Synthetic waterproofing covering, particularly for roofs, and method for manufacturing |
EP2108626A1 (fr) * | 2008-04-11 | 2009-10-14 | Electricité de France | Produit d'isolation thermique a base de laine minerale et de poudre metallique a faible emissivite |
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WO2010048187A1 (en) * | 2008-10-20 | 2010-04-29 | Basf Corporation | Roofing materials with metallic appearance |
FR3017149A1 (fr) * | 2014-01-31 | 2015-08-07 | Decathlon Sa | Dispositif de protection solaire |
WO2015114253A1 (fr) * | 2014-01-31 | 2015-08-06 | Decathlon | Dispositif de protection solaire |
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US20180311943A1 (en) * | 2015-10-28 | 2018-11-01 | Madico, Inc. | Multilayer composite films for architectural applications |
US10751973B2 (en) | 2016-03-21 | 2020-08-25 | Saint-Gobain Performance Plastics Corporation | Architectural membrane |
US20190308142A1 (en) * | 2016-08-26 | 2019-10-10 | Taiyo Kogyo Corporation | Fluororesin film material and production process therefor |
CN112601661A (zh) * | 2018-08-23 | 2021-04-02 | 美国西幔公司 | 具有透光性和拉伸性的多层复合材料 |
Also Published As
Publication number | Publication date |
---|---|
EP1313923A2 (en) | 2003-05-28 |
JP2004507386A (ja) | 2004-03-11 |
AU2001279236A1 (en) | 2002-03-13 |
WO2002018133A3 (en) | 2002-04-18 |
CA2418005A1 (en) | 2002-03-07 |
DE10042464A1 (de) | 2002-03-28 |
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