CA2150466C - Gas permeable materials - Google Patents
Gas permeable materialsInfo
- Publication number
- CA2150466C CA2150466C CA 2150466 CA2150466A CA2150466C CA 2150466 C CA2150466 C CA 2150466C CA 2150466 CA2150466 CA 2150466 CA 2150466 A CA2150466 A CA 2150466A CA 2150466 C CA2150466 C CA 2150466C
- Authority
- CA
- Canada
- Prior art keywords
- gas permeable
- permeable material
- formaldehyde resin
- reaction product
- substrate
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 50
- -1 perfluoroalkyl alcohol Chemical compound 0.000 claims abstract description 23
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 239000011152 fibreglass Substances 0.000 claims 1
- 239000004745 nonwoven fabric Substances 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 239000012528 membrane Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- RNMCQEMQGJHTQF-UHFFFAOYSA-N 3,5,6,7-tetrahydrotetrazolo[1,5-b][1,2,4]triazine Chemical compound N1CCN=C2N=NNN21 RNMCQEMQGJHTQF-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical group OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 229940048879 dl tartaric acid Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000002960 lipid emulsion Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
- B01D39/083—Filter cloth, i.e. woven, knitted or interlaced material of organic material
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
- A41D31/102—Waterproof and breathable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1692—Other shaped material, e.g. perforated or porous sheets
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
- D04H1/68—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions the bonding agent being applied in the form of foam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
- B01D2239/0428—Rendering the filter material hydrophobic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
- Y10T428/31544—Addition polymer is perhalogenated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31906—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
- Y10T442/184—Nonwoven scrim
- Y10T442/198—Coated or impregnated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2164—Coating or impregnation specified as water repellent
- Y10T442/2172—Also specified as oil repellent
Abstract
A gas permeable material having pores through it, in which the pore interiors are coated with the reaction product of a) an ester of a perfluoroalkyl alcohol and a poly-basic hydroxyl-carboxylic acid, and b) a melamine formsldehyde, urea-formaldehyde, or glycol modified formaldehyde. The material is oleophobic and is useful in filtration applictions and in garments.
Description
215û46(~
wo 94/13385 1 PCTAJS93/0492 TITLE OF THE INVENTION
Gas Permeable Materials FIELD OF THE INVENTION
i This invention relates to gas permeable materials that are hydrophobic and oleophobic. More particularly, the invention relates to materials coated with a composition that is hydrophobic and oleophobic for use in filtration and in garment constructions.
BACKGROUND OF THE INVENTION
There is a need for gas permeable materials having enhanced lo oleophobic and hydrophobic properties.
Gas filters and vent filters have been made from porous materials including porous polymers, such as porous polyolefins or polytetrafluoroethylene. However, the oleophobicity and hydrophobicity of such materials needs to be enhanced. For example, lack of oleophobicity has impaired use of such materials as gas filters in uses involving engines or devices that are commonly exposed to oil in the surrounding environment.
Moreover, thin flexible laminates containing porous films or membranes are useful in garment constructions, and oil and water 20 repellancy is sometimes desirable.
SUMMARY OF THE INVENTION
The product of this invention is a flexible gas permeable material which comprises a substrate which has passageways, or - continuous pores, through the substrate, and a coating on at least 25 a portion of the interior of the passageways which is the reaction product of:
A. an ester of a perfluoroalkyl alcohol of 4-24 carbon atoms and a poly-basic hydroxyl-containing carboxylic acid of 2-6 carbon atoms, -2150~66 and B. a resin material selected from the class consisting of melamine formaldehyde resin, urea-formaldehyde resin, and glycol modified formaldehyde resin.
The process of the invention comprises coating a gas permeable material which has passageways through the material with a mixture of A and B described above, and crosslinking the mixture.
By continuous pores or passageways is meant that the material has interstices that comprise continuous interconnecting passageways extending through the thickness of the material so that the passageways open on both sides.
The coating coats a portion of the surface of the pores but does not block the pores. Thus, the gas permeability property of the gas permeable material remains intact and the material is useful as a filter to pass gas therethrough. The presence of the coating renders the material more oleophobic than the material without the coating.
DESCRIPTION OF THE INVENTION
The gas permeable material can be any material that allows passage of gas, especially air. It is a material that contains interstices that comprise continuous passages extending through the thickness of the material. The passageways open on both sides.
Preferably the material is flexible and is in sheet, tube, or plug form. The material can be a fabric, such as a nonwoven, woven, or knit fabric, or a scrim. The material can be made of paper such as filter paper, or a cloth. The material can also be a porous polymeric film or membrane, synthetic or natural, where the pores form the interstices or passageways. Representative polymers useful in the material include polyamide, polyurethane, polyester, 30 polyvinylidene fluoride, polyacrylic, polyolefins such as polyethylene and polypropylene, and the like. The material will generally be from about 1 to about 200 micrometers thick.
Preferred as a gas permeable filter material is porous polytetrafluoroethylene (PTFE), especially microporous expanded 21 50 16~
polytetrafluoroethylene membrane sheet made as described in U.S.
Patent 3,953,566 which has a microstructure of nodes interconnected with fibrils. The resulting micropores or voids allow for good gas or air flow while providing liquid water resistance. These porous PTFE membranes preferably have a Gurley number of between 0.1 second and 80 seconds, depending on pore size and pore volume.
The esterification products are the reaction products of a perfluorinated alcohol and a polybasic carboxylic acid having hydroxyl functionality. The perfluorinated alcohols useful to make the esterification product in the coating material are of the general formula Rf(CH2)nOH
wherein Rf is perfluoroalkyl, linear or branched, of between 4 and 24 carbon atoms, and n is an integer from 1 to 12. Representative Rf groups include C4Fg-, C24F4g-, and the like. A preferred alcohol is a mixture of F(CF2)n(CH2)20H where n is 6, 8, 10, 12 and 14. Polybasic acids includes di- and tri-basic alkyl carboxylic acids. For example, one such acid is citric acid, which has the formula HOOC-C-OH
The complete esterification of citric acid is difficult to obtain because stearic hindrance inhibits esterification of the middle COOH group to aid in esterifying the hindered -COOH group, an epoxide is sometimes added to the reaction mix. An especially preferred polybasic acid is malic acid, which has the formula HOOC-CH-OH
or tartaric acid, which has the formula HOOC-CH-OH
HOOC-CH-OH.
The alcohol or the ester is then reacted with a crosslinking agent such as a melamine formaldehyde resin, or a urea-formaldehyde, or a glycol modified formaldehyde resins.
wo 94/13385 1 PCTAJS93/0492 TITLE OF THE INVENTION
Gas Permeable Materials FIELD OF THE INVENTION
i This invention relates to gas permeable materials that are hydrophobic and oleophobic. More particularly, the invention relates to materials coated with a composition that is hydrophobic and oleophobic for use in filtration and in garment constructions.
BACKGROUND OF THE INVENTION
There is a need for gas permeable materials having enhanced lo oleophobic and hydrophobic properties.
Gas filters and vent filters have been made from porous materials including porous polymers, such as porous polyolefins or polytetrafluoroethylene. However, the oleophobicity and hydrophobicity of such materials needs to be enhanced. For example, lack of oleophobicity has impaired use of such materials as gas filters in uses involving engines or devices that are commonly exposed to oil in the surrounding environment.
Moreover, thin flexible laminates containing porous films or membranes are useful in garment constructions, and oil and water 20 repellancy is sometimes desirable.
SUMMARY OF THE INVENTION
The product of this invention is a flexible gas permeable material which comprises a substrate which has passageways, or - continuous pores, through the substrate, and a coating on at least 25 a portion of the interior of the passageways which is the reaction product of:
A. an ester of a perfluoroalkyl alcohol of 4-24 carbon atoms and a poly-basic hydroxyl-containing carboxylic acid of 2-6 carbon atoms, -2150~66 and B. a resin material selected from the class consisting of melamine formaldehyde resin, urea-formaldehyde resin, and glycol modified formaldehyde resin.
The process of the invention comprises coating a gas permeable material which has passageways through the material with a mixture of A and B described above, and crosslinking the mixture.
By continuous pores or passageways is meant that the material has interstices that comprise continuous interconnecting passageways extending through the thickness of the material so that the passageways open on both sides.
The coating coats a portion of the surface of the pores but does not block the pores. Thus, the gas permeability property of the gas permeable material remains intact and the material is useful as a filter to pass gas therethrough. The presence of the coating renders the material more oleophobic than the material without the coating.
DESCRIPTION OF THE INVENTION
The gas permeable material can be any material that allows passage of gas, especially air. It is a material that contains interstices that comprise continuous passages extending through the thickness of the material. The passageways open on both sides.
Preferably the material is flexible and is in sheet, tube, or plug form. The material can be a fabric, such as a nonwoven, woven, or knit fabric, or a scrim. The material can be made of paper such as filter paper, or a cloth. The material can also be a porous polymeric film or membrane, synthetic or natural, where the pores form the interstices or passageways. Representative polymers useful in the material include polyamide, polyurethane, polyester, 30 polyvinylidene fluoride, polyacrylic, polyolefins such as polyethylene and polypropylene, and the like. The material will generally be from about 1 to about 200 micrometers thick.
Preferred as a gas permeable filter material is porous polytetrafluoroethylene (PTFE), especially microporous expanded 21 50 16~
polytetrafluoroethylene membrane sheet made as described in U.S.
Patent 3,953,566 which has a microstructure of nodes interconnected with fibrils. The resulting micropores or voids allow for good gas or air flow while providing liquid water resistance. These porous PTFE membranes preferably have a Gurley number of between 0.1 second and 80 seconds, depending on pore size and pore volume.
The esterification products are the reaction products of a perfluorinated alcohol and a polybasic carboxylic acid having hydroxyl functionality. The perfluorinated alcohols useful to make the esterification product in the coating material are of the general formula Rf(CH2)nOH
wherein Rf is perfluoroalkyl, linear or branched, of between 4 and 24 carbon atoms, and n is an integer from 1 to 12. Representative Rf groups include C4Fg-, C24F4g-, and the like. A preferred alcohol is a mixture of F(CF2)n(CH2)20H where n is 6, 8, 10, 12 and 14. Polybasic acids includes di- and tri-basic alkyl carboxylic acids. For example, one such acid is citric acid, which has the formula HOOC-C-OH
The complete esterification of citric acid is difficult to obtain because stearic hindrance inhibits esterification of the middle COOH group to aid in esterifying the hindered -COOH group, an epoxide is sometimes added to the reaction mix. An especially preferred polybasic acid is malic acid, which has the formula HOOC-CH-OH
or tartaric acid, which has the formula HOOC-CH-OH
HOOC-CH-OH.
The alcohol or the ester is then reacted with a crosslinking agent such as a melamine formaldehyde resin, or a urea-formaldehyde, or a glycol modified formaldehyde resins.
2 1 ~ O ~ 6 Melamine is an acrylic amine of the formula C3H6N6, i.e., N N
~ N
The melamine formaldehyde resins are the reaction products of u melamine and formaldehyde (HCH0). They can contain several methylol groups per molecule, since the methylol content depends on o the melamine/formaldehyde ratio and on the reaction conditions.
The simplest reaction product is trimethylolmelamine "C~
N N
1~
HOH2CHN-C ~ C-NHCH20H
The coating mixture is prepared by simply mixing the esterification product with the crosslinking material in a suitable solvent, such as a ketone, such as acetone, or an alkyl alcohol, such as 2-propanol, or water-based emulsion of the material. The concentration of materials in the solvent will depend on the loadings desired.
The coating solution is applied by any convenient means to the porous filter material and spread uniformly over the material. Dip coating or spraying can be used so as to coat the pore walls but not block them. The solvent is then evaporated by any convenient means, and then heat curing is carried out to form the necessary crosslinked material.
The materials used to form the gas permeable substrates and used to form the coating may contain various other additive ingredients to impart specific properties to the product or as a process aid. For example, they may include ultraviolet light stabilizers, bacteriostats, and the like.
The coating imparts increased hydrophobic and oleophobic properties to the coated product, and the resulting coated materials exhibit unusually good hydrophobic and oleophobic properties while having good gas or air flow through the material.
The resulting coated material can be used in applications involving 21504~6 ~WO 94/13385 ~ 5 ~ PCT/US93/04921 gas flow where the material should be resistant to penetration by water, oil, or lipid emulsions. Such applications include use in waterproof, breathable fabrics, and gas vents or filters that protect electronic equipment used in or near automotive engines and the like. Useful applications also include medical devices where venting filters are needed, and in industrial filtration, where venting filters are needed, where oil mists are present.
The coated materials are also useful in medical vents where oil or fatty substances in parental drip bottles can clog gas vents.
EXAMPLES
ExamPle 1 TWD coated products (A and B) were prepared as follows:
(A) 3g of perfluoroalkylcitrate (Zonyl TBC) obtained from the DuPont Company was mixed with 0.6 9 melamine formaldehyde resin (Aerotex 3030, American Cyanamid), 0.15 9 catalyst (Aerotex DC, American Cyanamid), and 60 g Freon-TF (DuPont) and 59 2-propanol.
An expanded porous PTFE membrane (ePTFE) was dipped into the mixture. The coated membrane was air dried, then placed in an oven at 170~C for 2 minutes to complete the curing step.
(B) Perfluoroalkylcitrate (Zonyl TBC) was mixed with perfluoroalkyl epoxide (Zonyl TE, DuPont) (wt. ratio 3:1) at 100~C
for 4 hours. Then 3 g of that product without any purification were mixed with 0.6 9 melamine formaldehyde resin (Aerotex 3730, American Cyanamid), 0.15 9 catalyst (Aerotex DC, American Cyanamid), and 60 g Freon-TF (DuPont) and 5g 2-propanol. The coating and curing steps were carried out the same way as in part (A).
The membrane used was obtained from W. L. Gore & Associates, Inc. and was about 20cm by 20cm and about 0.005 cm thick.
215~4~6 Test Results:
Oil Ratinq In these tests, oil rating was carried out by AATCC Test Method 118-1983. The higher the number, the better the oil t s repellency.
The tests for gasoline, engine cleaner, motor oil, methanol, acetone and transmission fluid were carried out by the same procedure as the oil rating test, but using the fluid specified.
The test temperature was as indicated. The time a drop of fluid was on the coated material was five minutes, after which the "repel" or "wet" condition was observed and recorded. By "repel"
is meant that the drop did not noticeably spread.
Uncoated ExamPle ExamDle TemDeratureePTFE (A) (B) Oil Rating 1 8 8 Gasoline (Mobil, Reg.
unleaded) 25~C wet repel repel Engine Cleaner (prestone) 70~C wet wet repel Motor Oil (Quaker) 25~C wet repel repel Methanol 25~C wet repel repel Acetone 25~C wet wet repel Transmission Fluid (CASTROL, 70~C wet repel repel Type F) 3s Gurley Numbers were obtained as follows:
The resistance of samples to air flow was measured by a Gurley densometer (ASTM D726-58) manufactured by W. & L. E. Gurley & Sons. The results are reported in terms of Gurley number which is the time in seconds for 100 cubic centimeters of air to pass through 1 square inch of a test sample at a pressure drop of 4.88 inches of water.
The Water Entry Pressure (WEP) was measured following the Quality Control Test Method No. 584 of W. L. Gore & Associates, w 2 1 ~
0 94/1338S - ~ - PCT/US93/04921 Inc. The WEP tester used is manufactured by Gore. Test sample is clamped between a pair of testing plates taking care not to cause damage. The lower plate has the ability to pressurize a section of the sample with water. A piece of pH paper is placed on top of the sample between the plate on the non-pressurized side as an indicator of evidence for water entry. The sample is then pressurized in small increments, waiting 10 seconds after each pressure change until a color change in the pH paper indicates the first signs of water entry. The water pressure at breakthrough or entry is recorded as the Water Entry Pressure. The test results are taken from the center of test sample to avoid erroneous results that may occur from damaged edges.
Water entry pressure below 2 psi was measured with an apparatus based upon the above WEP tester with modifications for low pressure. A sample with pH paper is held in a 25 mm clear filter holder obtained from Nuclepore Corporation, such that one side of the membrane can be pressurized with water. Water column is applied to the sample in gradual increments until a color change appears in the pH paper. The height of the water column is recorded and converted to psi.
Results were:
Uncoated Example Example ePTFE (A) IB) Gurley (seconds) 8 14 14 Water Entry Pressure >10 psi >10 psi >10 psi ExamPle 2 (A) Perfluoroalkylalcohol (Zonyl BA-N) was reacted with DL
malic acid (Aldrich) at a mole ratio 1.2:1.0 at 180~ for 8 hours using toluene sulfonic acid (0.5X wt based on Zonyl BA-N) as catalyst. 1 9 of the reaction product was dissolved in 20 9 Freon-TF and acetone (1:1 wt ratio) that contained 0.2 9 melamine 215~
formaldehyde resin (Aerotex 3030) and 0.01 9 Aerotex 4040 (catalyst), at ordinary room conditions. An expanded porous polytetrafluoroethylene membrane was dipped in the solution, air dried, and oven cured at 170~C for 2 minutes. The coated membrane s was ready for testing. A piece of nylon taslite fabric was also f dipped in the solution, air dried, and oven cured at 170~ for 2 minutes. This fabric was ready for testing.
(B) Perfluoroalkyl alcohol (Zonyl BA-N) was reacted with DL
tartaric acid (Aldrich) at a mole ratio of 1.2:1.0, under the same condition as in Example 2A, and then 19 of the reaction product was dissolved in 209 Freon TF and acetone (1:1 wt ratio) that contained 0.29 melamine formaldehyde resin (Aerotex 3030) and 0.019 Aerotex 4040 (catalyst), at ordinary room conditions. A piece of ePTFE
membrane and a piece of nylon taslite fabric were each coated in the solution the same way as in Example 2A. The membrane and the fabric were ready for testing.
Test Results:
coated coated coated coated membrane fabric membrane fabric oil rating 8 8 8 8 Gurley (secs) 12 - 13 - means "not measured"
Each test was carried out as in Example 1.
~ N
The melamine formaldehyde resins are the reaction products of u melamine and formaldehyde (HCH0). They can contain several methylol groups per molecule, since the methylol content depends on o the melamine/formaldehyde ratio and on the reaction conditions.
The simplest reaction product is trimethylolmelamine "C~
N N
1~
HOH2CHN-C ~ C-NHCH20H
The coating mixture is prepared by simply mixing the esterification product with the crosslinking material in a suitable solvent, such as a ketone, such as acetone, or an alkyl alcohol, such as 2-propanol, or water-based emulsion of the material. The concentration of materials in the solvent will depend on the loadings desired.
The coating solution is applied by any convenient means to the porous filter material and spread uniformly over the material. Dip coating or spraying can be used so as to coat the pore walls but not block them. The solvent is then evaporated by any convenient means, and then heat curing is carried out to form the necessary crosslinked material.
The materials used to form the gas permeable substrates and used to form the coating may contain various other additive ingredients to impart specific properties to the product or as a process aid. For example, they may include ultraviolet light stabilizers, bacteriostats, and the like.
The coating imparts increased hydrophobic and oleophobic properties to the coated product, and the resulting coated materials exhibit unusually good hydrophobic and oleophobic properties while having good gas or air flow through the material.
The resulting coated material can be used in applications involving 21504~6 ~WO 94/13385 ~ 5 ~ PCT/US93/04921 gas flow where the material should be resistant to penetration by water, oil, or lipid emulsions. Such applications include use in waterproof, breathable fabrics, and gas vents or filters that protect electronic equipment used in or near automotive engines and the like. Useful applications also include medical devices where venting filters are needed, and in industrial filtration, where venting filters are needed, where oil mists are present.
The coated materials are also useful in medical vents where oil or fatty substances in parental drip bottles can clog gas vents.
EXAMPLES
ExamPle 1 TWD coated products (A and B) were prepared as follows:
(A) 3g of perfluoroalkylcitrate (Zonyl TBC) obtained from the DuPont Company was mixed with 0.6 9 melamine formaldehyde resin (Aerotex 3030, American Cyanamid), 0.15 9 catalyst (Aerotex DC, American Cyanamid), and 60 g Freon-TF (DuPont) and 59 2-propanol.
An expanded porous PTFE membrane (ePTFE) was dipped into the mixture. The coated membrane was air dried, then placed in an oven at 170~C for 2 minutes to complete the curing step.
(B) Perfluoroalkylcitrate (Zonyl TBC) was mixed with perfluoroalkyl epoxide (Zonyl TE, DuPont) (wt. ratio 3:1) at 100~C
for 4 hours. Then 3 g of that product without any purification were mixed with 0.6 9 melamine formaldehyde resin (Aerotex 3730, American Cyanamid), 0.15 9 catalyst (Aerotex DC, American Cyanamid), and 60 g Freon-TF (DuPont) and 5g 2-propanol. The coating and curing steps were carried out the same way as in part (A).
The membrane used was obtained from W. L. Gore & Associates, Inc. and was about 20cm by 20cm and about 0.005 cm thick.
215~4~6 Test Results:
Oil Ratinq In these tests, oil rating was carried out by AATCC Test Method 118-1983. The higher the number, the better the oil t s repellency.
The tests for gasoline, engine cleaner, motor oil, methanol, acetone and transmission fluid were carried out by the same procedure as the oil rating test, but using the fluid specified.
The test temperature was as indicated. The time a drop of fluid was on the coated material was five minutes, after which the "repel" or "wet" condition was observed and recorded. By "repel"
is meant that the drop did not noticeably spread.
Uncoated ExamPle ExamDle TemDeratureePTFE (A) (B) Oil Rating 1 8 8 Gasoline (Mobil, Reg.
unleaded) 25~C wet repel repel Engine Cleaner (prestone) 70~C wet wet repel Motor Oil (Quaker) 25~C wet repel repel Methanol 25~C wet repel repel Acetone 25~C wet wet repel Transmission Fluid (CASTROL, 70~C wet repel repel Type F) 3s Gurley Numbers were obtained as follows:
The resistance of samples to air flow was measured by a Gurley densometer (ASTM D726-58) manufactured by W. & L. E. Gurley & Sons. The results are reported in terms of Gurley number which is the time in seconds for 100 cubic centimeters of air to pass through 1 square inch of a test sample at a pressure drop of 4.88 inches of water.
The Water Entry Pressure (WEP) was measured following the Quality Control Test Method No. 584 of W. L. Gore & Associates, w 2 1 ~
0 94/1338S - ~ - PCT/US93/04921 Inc. The WEP tester used is manufactured by Gore. Test sample is clamped between a pair of testing plates taking care not to cause damage. The lower plate has the ability to pressurize a section of the sample with water. A piece of pH paper is placed on top of the sample between the plate on the non-pressurized side as an indicator of evidence for water entry. The sample is then pressurized in small increments, waiting 10 seconds after each pressure change until a color change in the pH paper indicates the first signs of water entry. The water pressure at breakthrough or entry is recorded as the Water Entry Pressure. The test results are taken from the center of test sample to avoid erroneous results that may occur from damaged edges.
Water entry pressure below 2 psi was measured with an apparatus based upon the above WEP tester with modifications for low pressure. A sample with pH paper is held in a 25 mm clear filter holder obtained from Nuclepore Corporation, such that one side of the membrane can be pressurized with water. Water column is applied to the sample in gradual increments until a color change appears in the pH paper. The height of the water column is recorded and converted to psi.
Results were:
Uncoated Example Example ePTFE (A) IB) Gurley (seconds) 8 14 14 Water Entry Pressure >10 psi >10 psi >10 psi ExamPle 2 (A) Perfluoroalkylalcohol (Zonyl BA-N) was reacted with DL
malic acid (Aldrich) at a mole ratio 1.2:1.0 at 180~ for 8 hours using toluene sulfonic acid (0.5X wt based on Zonyl BA-N) as catalyst. 1 9 of the reaction product was dissolved in 20 9 Freon-TF and acetone (1:1 wt ratio) that contained 0.2 9 melamine 215~
formaldehyde resin (Aerotex 3030) and 0.01 9 Aerotex 4040 (catalyst), at ordinary room conditions. An expanded porous polytetrafluoroethylene membrane was dipped in the solution, air dried, and oven cured at 170~C for 2 minutes. The coated membrane s was ready for testing. A piece of nylon taslite fabric was also f dipped in the solution, air dried, and oven cured at 170~ for 2 minutes. This fabric was ready for testing.
(B) Perfluoroalkyl alcohol (Zonyl BA-N) was reacted with DL
tartaric acid (Aldrich) at a mole ratio of 1.2:1.0, under the same condition as in Example 2A, and then 19 of the reaction product was dissolved in 209 Freon TF and acetone (1:1 wt ratio) that contained 0.29 melamine formaldehyde resin (Aerotex 3030) and 0.019 Aerotex 4040 (catalyst), at ordinary room conditions. A piece of ePTFE
membrane and a piece of nylon taslite fabric were each coated in the solution the same way as in Example 2A. The membrane and the fabric were ready for testing.
Test Results:
coated coated coated coated membrane fabric membrane fabric oil rating 8 8 8 8 Gurley (secs) 12 - 13 - means "not measured"
Each test was carried out as in Example 1.
Claims (7)
1. A flexible gas permeable material which comprises a substrate that contains passageways through the substrate, and a coating on at least a portion of the interior of the passageways, which is the crosslinked reaction product of a) an ester of a perfluoroalkyl alcohol of the formula Rf-(CH2)nOH
wherein Rf is perfluoroalkyl of 4-24 carbons and n is an integer of between 1 and 12, and a poly-basic hydroxyl-containing carboxylic acid of 2-6 carbon atoms and b) a crosslinking resin selected from the class consisting of melamine formaldehyde resin, urea-formaldehyde resin, and glycol modified formaldehyde resin.
wherein Rf is perfluoroalkyl of 4-24 carbons and n is an integer of between 1 and 12, and a poly-basic hydroxyl-containing carboxylic acid of 2-6 carbon atoms and b) a crosslinking resin selected from the class consisting of melamine formaldehyde resin, urea-formaldehyde resin, and glycol modified formaldehyde resin.
2. The gas permeable material of Calim 1 wherein the substrate is a sheet selected from the class consisting of woven fabric, nonwoven fabric, knit fabric, porous polymeric sheets, cellulosic papers, and fiberglass papers.
3. The gas permeable material of Claim 2 wherein the substrate is expanded porous polytetrafluoroethylene (PTFE).
4. The gas permeable material of claim 1 or 3 wherein component b) of the reaction product is melamine formaldhyde resin.
5. The gas permeable material of Claim 1 or 3 wherein in the reaction product, in the ester, the polybasic hydroxyl-containing carboxylic acid is malic acid or tartaric acid, and the crosslinking resin is selected from the class consisting of melamine formaldehyde resin and urea formaldehyde resin.
6. The gas permeable material of Claim 1 or 3 wherein in the reaction product, the ester is perfluoroalkyl citrate.
7. Process comprising placing the material defined in Claim 1 in a filter holder and subjecting the combination so obtained to a stream of gas.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/990,224 US5242747A (en) | 1992-12-14 | 1992-12-14 | Gas permeable materials |
US07/990,224 | 1992-12-14 | ||
FR9314716A FR2713230A1 (en) | 1992-12-14 | 1993-12-08 | Gas permeable material |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2150466A1 CA2150466A1 (en) | 1994-06-23 |
CA2150466C true CA2150466C (en) | 1998-12-08 |
Family
ID=26230793
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2150466 Expired - Fee Related CA2150466C (en) | 1992-12-14 | 1993-05-25 | Gas permeable materials |
Country Status (7)
Country | Link |
---|---|
US (1) | US5242747A (en) |
EP (1) | EP0673278B1 (en) |
AU (1) | AU4389293A (en) |
CA (1) | CA2150466C (en) |
FR (1) | FR2713230A1 (en) |
IT (1) | ITTO930941A1 (en) |
WO (1) | WO1994013385A1 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2237810T3 (en) * | 1993-03-26 | 2005-08-01 | W.L. GORE & ASSOCIATES, INC. | USE IN GARMENTS OF A POLYETRAFLUOROETHYLENE ARTICLE WITH COVERING. |
US5645627A (en) * | 1995-02-28 | 1997-07-08 | Hollingsworth & Vose Company | Charge stabilized electret filter media |
ITPI950062U1 (en) * | 1995-11-11 | 1997-05-11 | Euro Foam Di Bonalumi Giulio E | STRAPS FOR PADDING, OF ANY SHAPE AND SIZE, IN FLEXIBLE MELAMINE RESIN |
JP3219700B2 (en) * | 1996-09-18 | 2001-10-15 | 日東電工株式会社 | Vent filter member |
JP3825632B2 (en) | 1998-09-08 | 2006-09-27 | ブルックウッド・カンパニーズ・インコーポレイテッド | Breathable and waterproof laminate and method for producing the same |
US6676993B2 (en) * | 1999-02-12 | 2004-01-13 | Bha Technologies, Inc. | Porous membrane structure and method |
US6228477B1 (en) * | 1999-02-12 | 2001-05-08 | Bha Technologies, Inc. | Porous membrane structure and method |
AU2001237000A1 (en) | 2000-02-15 | 2001-08-27 | Hollingsworth And Vose Company | Melt blown composite hepa filter media and vacuum bag |
FR2807825B1 (en) * | 2000-04-14 | 2002-08-30 | Total Raffinage Distribution | DEVICE FOR SEPARATING A LUBRICATING OIL FROM A REFRIGERANT GAS IN A REFRIGERANT CIRCUIT WITH A COMPRESSOR |
WO2002089956A1 (en) * | 2001-05-02 | 2002-11-14 | Hollingsworth & Vose Company | Filter media with enhanced stiffness and increased dust holding capacity |
US6723040B2 (en) * | 2001-08-20 | 2004-04-20 | International Development Consultants | Bowel probe & method for controlling bowel incontinence |
US20030203696A1 (en) * | 2002-04-30 | 2003-10-30 | Healey David Thomas | High efficiency ashrae filter media |
US6802808B2 (en) * | 2002-08-16 | 2004-10-12 | International Development Consultants, A Proprietorship Of Wichita, Kansas | Bowel probe system & method for controlling bowel incontinence |
PL1885476T3 (en) * | 2005-05-25 | 2016-05-31 | Gore & Ass | Multi-functional coatings on microporous substrates |
US20100006483A1 (en) * | 2008-07-10 | 2010-01-14 | Ravi Yekula | Replaceable filter elements including unique pressure relief and systems including same |
US20100212272A1 (en) * | 2009-02-24 | 2010-08-26 | Hollingsworth & Vose Company | Filter media suitable for ashrae applications |
DE112015001545T5 (en) * | 2014-03-31 | 2016-12-22 | Trane International Inc. | Repellent / absorbent structures in cooling systems and liquid vapor deposition in cooling systems |
CN106947106A (en) * | 2017-03-21 | 2017-07-14 | 亚美滤膜(南通)有限公司 | Oleophobic property high molecule plastic and its oleophobic property processing method |
CN113069832B (en) * | 2021-04-07 | 2022-01-11 | 天台宏辉过滤科技有限公司 | Hydrophobic anti-blocking wear-resistant industrial filter cloth and preparation method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2607494A (en) * | 1949-06-16 | 1952-08-19 | Paper Patents Co | Filter element |
US3923715A (en) * | 1973-07-26 | 1975-12-02 | Du Pont | Aqueous dispersions of perfluoroalkyl esters and vinyl polymers for treating textiles |
US4014857A (en) * | 1974-12-06 | 1977-03-29 | E. I. Du Pont De Nemours & Co. | Fluorinated oily soil release agents |
US4029585A (en) * | 1975-07-26 | 1977-06-14 | E. I. Du Pont De Nemours And Company | Aqueous dispersions of perfluoroalkyl esters for treating textiles |
US5096473A (en) * | 1991-03-01 | 1992-03-17 | W. L. Gore & Associates, Inc. | Filtration fabric laminates |
-
1992
- 1992-12-14 US US07/990,224 patent/US5242747A/en not_active Expired - Fee Related
-
1993
- 1993-05-25 AU AU43892/93A patent/AU4389293A/en not_active Abandoned
- 1993-05-25 EP EP19930914114 patent/EP0673278B1/en not_active Expired - Lifetime
- 1993-05-25 WO PCT/US1993/004921 patent/WO1994013385A1/en active IP Right Grant
- 1993-05-25 CA CA 2150466 patent/CA2150466C/en not_active Expired - Fee Related
- 1993-12-08 FR FR9314716A patent/FR2713230A1/en not_active Withdrawn
- 1993-12-13 IT ITTO930941 patent/ITTO930941A1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ITTO930941A0 (en) | 1993-12-13 |
FR2713230A1 (en) | 1995-06-09 |
US5242747A (en) | 1993-09-07 |
CA2150466A1 (en) | 1994-06-23 |
EP0673278B1 (en) | 1996-08-28 |
EP0673278A1 (en) | 1995-09-27 |
WO1994013385A1 (en) | 1994-06-23 |
AU4389293A (en) | 1994-07-04 |
ITTO930941A1 (en) | 1994-06-14 |
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