GB2157703A - Breathable, non-poromeric polyurethane films - Google Patents

Breathable, non-poromeric polyurethane films Download PDF

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Publication number
GB2157703A
GB2157703A GB08510024A GB8510024A GB2157703A GB 2157703 A GB2157703 A GB 2157703A GB 08510024 A GB08510024 A GB 08510024A GB 8510024 A GB8510024 A GB 8510024A GB 2157703 A GB2157703 A GB 2157703A
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polyurethane
molecular weight
low molecular
active hydrogen
hydrogen functionality
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GB2157703B (en
GB8510024D0 (en
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James Ronald Holker
George Robert Lomax
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Shirley Institute
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Shirley Institute
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A polyurethane which can be used to form a breathable non-poromeric film, is prepared from an isocyanate-terminated prepolymer and a polyol component containing at least 25% of polyoxyetheylene units and a low molecular weight constituent having an active hydrogen functionality of at least two, the prepolymer having been formed by reaction of a polyisocyanate with a low molecular weight component having an active hydrogen functionality of at least two. Uses: - Fabric coatings, film laminates or unsupported films.

Description

SPECIFICATION Breathable, non-poromeric polyurethane films This invention relates to breathable, non-poromeric polyurethane films Our British Patent Application No. 8037510 (Serial No.2087909) describes breathable, non-porous polyurethane films prepared by reaction of a prepolymerformed from a low molecular weight difunctional compound and an excess of a diisocyanate with polyethylene glycol. However, such films are sometimes rather stiff and inflexible with a high Young's Modulus and are, therefore, unsuitable for use in connection with some type of clothing.
The present invention has been made from a consideration of this problem.
We have discovered that by modifying the polyol component, that is to say the polyethylene glycol component, so as to reduce the hard/soft segment ratio but in such a way that the overall breathability of the film is not substantially altered the initial Young's Modulus can be lowered and a softer film obtained.
According to the invention there is provided a breathable, non-poromeric polyurethane formed from a reaction mixture comprising an isocyanate terminated prepolymer, a polyol component containing at least 25% by weight of polyoxyethylene units based on the total weight of constituents, and a low molecular weight constituent having an active hygrogen functionality of at least two, said prepolymer being formed from the reaction product of a polyisocyanate containing at least two isocyanate groups per molecule with a low molecular weight component having an active hydrogen functionality of at least two.
By the invention the viscosity of the reaction mixture is increased by addition of one or more further low molecular weight constituents having a functionality of at least two, preferably a trifunctional component, and which may be the same or different to the low molecular weight component used to form the prepolymer. This increase in viscosity can be obtained without adversely affecting the mechanical properties and breathability of the film. The product of the reaction of the prepolymer and the polyol component has unreacted isocyanate groups.
the further addition of a low molecularweight constituent having functionality of at least two increases the viscosity either by promoting more efficient chain extension or by increasing the degreee of chain branching. Some polyurethanes may have a certain degree of chain branching and hence those materials, when produced in accordance with the invention will have an even higher viscosity.
The polyisocyanate used in the invention may be any of those used for forming polyurethanes for example toluene -2,4-and toluene -2,6- (and mixtures thereof), 1,6-hexamethylene, 1,5-naphthalene-, 4,4'-diphenylmethane-, 1,4-cyclohexane-, 1,4phenylene, m- and p-tetramethylxylyl-diisocyanates and mixtures thereof. Preferred, however, are isophorone- and 4,4'-dicyclohexylmethanediisocyanate. Polymeric diisocyanates containing at least two isocyanate groups per molecule are also suitable.
The low molecular weight active hydrogen component having an active hydrogen functionality of at least two used to form the prepolymer may be a difunctional compound such as a diamine, dihydrazide, diamide, dithiol, dicarboxylic acid, disulphonic acid or mixtures thereof. Preferred, however, are diols such as thiodiglycol, ethylene glycol, diethylene glycol, and butane -1,4-diol. In addition to difunctional compounds, compounds with an active hydrogen functionality of three or more can be used.
Examples of trifunctional compounds includetriols such as trimethylolpropane, triamines such as diethylenetriamine, and compounds containing more than one type of functional group which may comprise, but is not restricted to, hydroxyl, amine, thiol, carboxylic acid, sulphonic acid, and imide groups. Mixtures of these compounds may also be used. Preferably, the molecular weight of the low molecular weight component is not more than 200.
The polyol component reacted with the prepolymer must be chosen so that the final polymer contains at least 25%, preferably from 25 to 45% of polyoxyethylene units. The preferred polyoxyethylenecontaining compound is polyethylene glycol, preferably of molecular weight greater than 400, more particularly within the range 400-2000, and more preferably within the range of 600-1500. Other oxyethylene containing compounds include block copolymers of ethylene oxide with other 1,2-alkylene oxides, such as propylene oxide, butylene oxide; and copolymers formed by reaction of ethylene oxide with polyhydroxy compounds, polyamines, and polythiols.
The polyol component may consist in part of substances not containing polyoxyethylene units, such as polyester polyols and polyether polyols.
Examples of polyester polyols containing at least two terminal hydroxyl groups are polycaprolactone diols and those dereived from polyols and organic di- or poly-carboxylic acids. Typical acids used for preparing polyester polyols include diacids such as oxalic, maleic, succinic, adipic, suberic, sebacic, and the isomeric phthalic acids. Polyols used for preparing polyester polyols include, ethylene glycol, diethylene glycol, butane-1 ,4-diol, 1 6-hexanediol and mixtures thereof, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose. A preferred polyether polyol is polytetramethylene glycol. The polyoxyethylene-containing compound and other polyols may be added to the prepolymer simultaneously or successively. Preferred, however, is successive addition with the polyoxyethylene containing compound added last.
The polyol component may comprise a mixture of polyols of different molecular weight. Preferably, when the polyol component comprises polyethylene glycol, the amount of polyethylene glycol is at least 25% and preferably not more than 45% by weight of the reaction mixture.
The low molecular weight constituent having an active hydrogen functionality of at least two may comprise a mixture of different compounds. The low molecular weight consistuent can comprise a com pound having an active hydrogen functionality of three, for example a triol such as trimethylol propane and can comprise compounds containing more than one type of functional group for example hydroxyl, amine, thiol, carboxylic acid, sulphonic acid and amide groups. In other words the low molecular weight constituent can be the same kind of substance as has been described herein as a low molecular weight component for forming the prepolymer. However, it is not necessary that the low molecular weight constituent and the low molecular weight component should be the same polyurethane formulation according to the invention.
If the proportions of reagent used in the preparation of the polyurethane are such that it still contains residual isocyanate groups, a low molecular weight component having a functionality of at least two can then be added to bring the isocyanate-active hydrogen ratio to unity and thereby increase the viscosity of the resulting polyurethane. Examples of viscosity modifiers or extenders include difunctional compounds such as diols and diamines and preferably trifunctional compounds such as triols, for example trimethylolpropane.
The polyurethanes prepared according to the present invention can be used as fabric coatings, film laminates or unsupported films for packaging or medical purposes. In addition, it is possible to improve the mechanical properties and solvent resistance of the polymers by addition of cross linking agents according to standard polyurethane technology. Typical cross linking agents are triisocyanates and melamine formaldehyde resins.
The following examples are illustrative of the invention: Example 1 Diethylene glycol (252.99) in ethyl acetate (250 cm3) was added slowly during 1.5h to a stirred solution of isophorone diisocyanate (11 76.5g), dibutyltin dilaurate. (1.1g), and ethyl acetate (1200 cm3) at 50"C. The mixture was stirred for a further 1 h, until the isocyanate content reached a constant level, and a solution of polycaprolactone diol, m.w. 830 (1092.89) in ethyl acetate (1100cm3) was was added over 1.0h and the reaction product heated at reflux temperature for 1.5h.Polyethylene glycol, m.w. 1000 (1190.79) in ethyl acetate (1200 cm3) was then added over 2.0h and the reaction mixture retained at reflux temperature for a further 1.ooh, when a solution of trimethylolpropane (35.51 g) was added over 0.5h.
After 1.5h an infrared spectrum of the reaction product showed that little isocyanate remained. The intrinsic viscosity of the resulting polymer, measured in dimethylformamide at 250C, was 0.60.
Cross-linked films of 25 microns thickness were obtained by casting an intimate mixture of the above reaction product (100 g) and ImprafixTH crosslinking agent (4.6 g) onto siliconised release paper, and drying and curing the polyurethane at 100or (residence time 0.1 - 0.3h).The resulting film had a breaking load of 10.5 MN/m2, elongation 879%, and intrinsic water vapour permeability of 121 g.mm/m2/ 24h.
A solution of the above reaction product containing 7% w/w Imprafix TH was coated onto woven, filament nylon fabric (120 g/m2) by the knife-over-roll technique. The coated fabric was then dried and cured at 100 C in two passes through the coating machine oven (total residence time approximately 0.2h). The water vapour permeability of the coated fabric (155 glum2), as measured by the Gore cup method, was 3182 g/m2/day.
Example 2 A prepolymer was prepared as in example 1 from 4,4'-diisocyanatodicyclohexylmethane, Desmodur W (37.39 g), diethyleneglycol (6.82), dibutyltin dilaurate (0.2 g) and a solvent mixture (45 cm3; 50/50 v/v) of dimethylformamide and toluene. Polycaprolactone diol, m.w. (18.90 g) in the mixed solvent (20 cm3) was then added dropwise during 0.4h to the prepolymer solution maintained at 70"C. After 2.0h, polyethylene glycol m.w. 1000 (32.11 g) in the solvent mixture (30 cm3) was added dropwise over 0.5h. After 2.5h, trimethylolpropane (0.95 g) in the mixed solvent (70 cm3) was added and the solution maintained at 80 C for 1.0 h. The intrinsic viscosity of the resulting polymer was 0.67.
Films cross-linked with 7% w/w of Imprafix TH had a breaking load of 46.7 MN/m2, elongation 578%, and intrinsic water vapour permeability of 71 g.
mm/m2/24 h.
Example 3 A prepolymer was prepared as in example 1 from 4,4'-diisocyanatodicylohexylmethane (527.9 g), diethylene glycol (160.4 g), dibutyltin diiaurate (1.5g), and dimethylformamide/toluene (20/80 v/v; 680 cm3). Polyethylene glycol, m.w. 1500 (528.9 g) in the mixed solvent (1100cm3) was was added to the prepolymer solution which was then maintained at 60 - 70 for 2.5 h. Trimethylolpropane (13.5 g) in the mixed solvent (1110 cm3)was finally added and heating continued until an infrared spectrum indicated no residual isocyanate. The intrinsic viscosity of the polymer was 0.91.
Films cross-linked with 7% w/w of Imprafix TH had a breaking load of 37.7 MN/m2, elongation 454 %.
Example 4 A prepolymer was prepared as in example 1 from 4,4'-diisocyanato-dicyclohexylmethane (50.60 g) diethyleneglycol (10.25 g), dibutyltin dilaurate (0.3 g), and methyl ethyl ketone (70 cm3). Polycaprolactone diol, m.w. 830 (48.10 g) in methyl ethyl ketone (50 cm3) was added over 0.6 h to the prepolymer solution maintained at 60"C. After 1.5 h Polyethylene glycol, m.w. 1000 (38.62 g) in methyl ethyl ketone (50 cm3) was added and heating continued until no isocyanate peak was observed in the infrared spectrum of the reaction product. The intrinsic viscosity of the polymer was 0.27.
Films cross-linked with 10% w/w Imprafix TH had a breaking load of 12.0 MN/m2, elongation 678%, and lintrinsic water vapour permeability of 102 g. mml /m2/ day.
Example 5 A prepolymer was prepared as in example 1 from toluene diisocyanate (80/20 ratio of 2,4- and 2,6 isomers, 29.96g), butane -1,4-diol (7.369), dibutyltin dilaurate (0.29) and a solvent mixture (30 cm3; 50/50 v/v) of dimethylformamide and toluene. Polycaprolactone diol, m.w. 993 (38.449) in the mixed solvent (40 cm3) was then added dropwise over a period of 0.5h, and the solution maintained at 600C.
Polyethylene glycol m.w. 1000 (38.719) in the mixed solvent (40 cm3) was added and the solution kept at 60"C for 0.5h. Finally, trimethylolpropane (1.1 5g) in the mixed solvent (5 cm3)was added and the solution was heated to 800for 10h.
The intrinsic viscosity of the resulting polymer was 0.32. Films cross linked with 7% w/w of Imprafix tH had a breaking load of 6.6 MN/M2, elongation 300 %, and intrinsic water vapour permeability of 282 g.
mm/m2/24hr.
Comparative example In order to demonstrate that the high water vapour transmission properties of these polyurethanes are specific for the polyethylene oxide structure, a polyurethane was prepared as in example 1, except that the polyethylene glycol m.w. 1000 component was replaced by a molar equivalent of polypropy leneglycol m.w. 1025.Thus,a prepolymerwas prepared as in example 1 from isophorone diisocyanate (25.619), diethylene glycol (5.52g), dibutyltin dilaurate (0.lg), and methyl ethyl ketone (28 cm3).
Polycaprolactone diol, m.w. 810 (23.29g) in methyl ethyl ketone (35 cm3) was added dropwise to the prepolymer solution maintained at reflux temperature. After 1.5h, polypropylene glycol, m.w. 1025 (26.529) in methyl ethyl ketone (37 cm3) was added dropwise over 0.5h and the solution kept under reflux for 2h. Trimethylolpropane (0.77g) in MEK (12 cm3) was then added and the reaction mixture maintained under reflux until an infrared spectrum of the product indicated that no isocyanate remained. The intrinsic viscosity of the polymer was 0.62.
Films cross-linked with 7% w/w of Imprafix TH had a breaking load of 9.6 MN/m2, elongation 531 %, and intrinsic water vapour permeability of only 17 g.
mm/m2/24h.
A carefully deaerated solution of the polypropylene glycol based polyurethane (45% solids in methyl ethyl ketone) containing 7% w/w Imprafix TH was coated onto a woven, filament nylon fabric (20 g/m2) by the knife-over-roll technique. The coated fabric was then dried and cured at 1 000C in two passed through the coating machine oven (total residence time 0.2h). The water vapour permeability (Gore cup method) of the coated fabric (156 g/m2) was only 317 g/m2/day.

Claims (23)

1. A breathable non-poromeric polyurethane formed from a reaction mixture comprising an isocyanate terminated prepolymer, a polyol component containing at least 25% by weight of polyoxyethylene units based on the total weight of constituents, and a low molecular weight constituent having an active hydrogen functionality of at least two, said prepolymer being formed from the reaction product of a polyisocyanate containing at least two isocyanate groups per molecule with a low molecular weight component having an active hydrogen functionality of at least two.
2. A polyurethane as claimed in Claim 1, wherein the low molecular weight component having an active hydrogen functionality of at least two is a polyol, a polyamide or a polyhydrazide.
3. A polyurethane as claimed in Claim 1 or Claim 2, wherein the low molecular weight component having an active hydrogen functionality of at least two contains different functional groups.
4. A polyurethane as claimed in Claim 3, wherein the low molecular weight component having an active hydrogen functionality of at least two contains an hydroxyl, amine, thiol, carboxylic acid, suiphonic acid, or amide group.
5. A polyurethane as claimed in any preceding claim wherein the prepolymer is formed from two or more low molecular weight components having an active hydrogen functionality of at least two.
6. A polyurethane as claimed in any preceding claim wherein two or more low molecular weight constituents having an active hydrogen functionality of at least two are reacted with the prepolymer.
7. A polyurethane as claimed in any preceding claim, wherein the polyol component comprises two or more polyols of different molecularweight.
8. A polyurethane as claimed in any preceding claim, wherein the polyol component comprises at least 25% by weight of polyethylene glycol based on the total weight of the reaction mixture.
9. A polyurethane as claimed in Claim 8, wherein the polyethylene glycol comprises two or more polyethylene glycols of different molecular weight.
10. A polyurethane as claimed in any of Claims 7 to 9 wherein the polyol comprises not more than 45% by weight of polyethylene glycol based on the weight of the reaction mixture.
11. A polyurethane as claimed in any of Claims 7 to 10, wherein the polyol comprises a mixture of polyethylene glycol and an hydroxyl terminated polyester.
12. A polyurethane as claimed in Claim 11, wherein the hydroxyl terminated polyester is a polycaprolactone diol having a molecular weight of from 500 to 2000.
13. A polyurethane as claimed in any preceding claim, wherein the low molecular weight constituent having an active hydrogen functionality of at least two is a triol.
14. A polyurethane as claimed in Claim 13, wherein the triol is trimethylol propane.
15. A polyurethane as claimed in any preceding claim, wherein the low molecular weight constituent having an active hydrogen functionality of at least two contains different functional groups.
16. A polyurethane as claimed in Claim 15, wherein the low molecular weight constituent having an active hydrogen functionality of at least two contains an hydroxyl, amine, thiol, carboxylic acid, sulphonic acid or amide group.
17. A polyurethane as claimed in any preceding claim, wherein the polyurethane is cross-linked.
18. A polyurethane as claimed in Claim 17, wherein cross linking is effected by addition of a cross linking agent to a solution of the polyurethane.
19. A polyurethane as claimed in Claim 18, wherein the cross linking agent is a triisocyanate.
20. A polyurethane as claimed in Claim 18, wherein the cross linking agent is a melamine formaldehyde resin.
21. A breathable, non-poromeric polyurethane substantially as described herein with reference to any one of the Examples.
22. A breathable film prepared by casting a solution of a polyurethane as claimed in any preceding claim and allowing the solvent to evaporate.
23. Afabric coated with a polyurethane as claimed in any of Claims 1 to 21.
GB08510024A 1984-04-19 1985-04-18 Breathable, non-poromeric polyurethane films Expired GB2157703B (en)

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GB848410263A GB8410263D0 (en) 1984-04-19 1984-04-19 Breathable non-poromeric polyurethane films

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4767825A (en) * 1986-12-22 1988-08-30 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
US4806598A (en) * 1986-12-22 1989-02-21 Kimberly-Clark Corporation Thermoplastic polymer blends and nonwoven webs prepared therefrom
US4820577A (en) * 1986-12-22 1989-04-11 Kimberly-Clark Corporation Meltblown superabsorbent thermoplastic compositions
US4847141A (en) * 1986-12-22 1989-07-11 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
EP0354981A2 (en) * 1988-07-16 1990-02-21 Firma Carl Freudenberg Process for the preparation of a liquid polyurethane-urea prepolymer and its further working-up to an open-pore reactive resin concrete
US4963638A (en) * 1988-02-26 1990-10-16 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
EP1388345A1 (en) * 2002-08-09 2004-02-11 The Procter & Gamble Company Polymeric compositions with enhanced vapour permeability and washability
EP1834993A1 (en) 2006-02-27 2007-09-19 Industrial Technology Research Institute Water-vapor permeable polyurethane-based films and textiles
WO2007107721A1 (en) * 2006-03-17 2007-09-27 Remploy Limited Air permeable, liquid impermeable barrier structure for protective garments
WO2008089016A1 (en) * 2007-01-12 2008-07-24 Ppg Industries Ohio, Inc. High impact interlayer for automotive window
US7709094B2 (en) 2007-10-05 2010-05-04 Industrial Technology Research Institute Co-extruded water-proof and moisture-permeable film structure and textile
US7732355B2 (en) 2005-12-27 2010-06-08 Industrial Technology Research Institute Water-vapor permeable films and textiles

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2087909A (en) * 1980-11-22 1982-06-03 Shirley Inst Breathable non-porous polyurethane film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2087909A (en) * 1980-11-22 1982-06-03 Shirley Inst Breathable non-porous polyurethane film

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4806598A (en) * 1986-12-22 1989-02-21 Kimberly-Clark Corporation Thermoplastic polymer blends and nonwoven webs prepared therefrom
US4820577A (en) * 1986-12-22 1989-04-11 Kimberly-Clark Corporation Meltblown superabsorbent thermoplastic compositions
US4847141A (en) * 1986-12-22 1989-07-11 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
US4767825A (en) * 1986-12-22 1988-08-30 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
US4963638A (en) * 1988-02-26 1990-10-16 Kimberly-Clark Corporation Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom
EP0354981A3 (en) * 1988-07-16 1991-04-17 Firma Carl Freudenberg Process for the preparation of a liquid polyurethane-urea prepolymer and its further working-up to an open-pore reactive resin concrete
EP0354981A2 (en) * 1988-07-16 1990-02-21 Firma Carl Freudenberg Process for the preparation of a liquid polyurethane-urea prepolymer and its further working-up to an open-pore reactive resin concrete
EP1388345A1 (en) * 2002-08-09 2004-02-11 The Procter & Gamble Company Polymeric compositions with enhanced vapour permeability and washability
WO2004014445A1 (en) * 2002-08-09 2004-02-19 The Procter & Gamble Company Polymeric compositions with enhanced vapour permeability
US7732355B2 (en) 2005-12-27 2010-06-08 Industrial Technology Research Institute Water-vapor permeable films and textiles
EP1834993A1 (en) 2006-02-27 2007-09-19 Industrial Technology Research Institute Water-vapor permeable polyurethane-based films and textiles
WO2007107721A1 (en) * 2006-03-17 2007-09-27 Remploy Limited Air permeable, liquid impermeable barrier structure for protective garments
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US7709094B2 (en) 2007-10-05 2010-05-04 Industrial Technology Research Institute Co-extruded water-proof and moisture-permeable film structure and textile

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GB2157703B (en) 1987-04-29
GB8510024D0 (en) 1985-05-30
GB8410263D0 (en) 1984-05-31

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Effective date: 19940418