CA2099104A1 - Polyvinyl chloride membrane composition and method for making a polyvinyl chloride membrane - Google Patents
Polyvinyl chloride membrane composition and method for making a polyvinyl chloride membraneInfo
- Publication number
- CA2099104A1 CA2099104A1 CA 2099104 CA2099104A CA2099104A1 CA 2099104 A1 CA2099104 A1 CA 2099104A1 CA 2099104 CA2099104 CA 2099104 CA 2099104 A CA2099104 A CA 2099104A CA 2099104 A1 CA2099104 A1 CA 2099104A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- membrane
- parts
- polyvinyl chloride
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 52
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 229920001897 terpolymer Polymers 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 239000008029 phthalate plasticizer Substances 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 239000000945 filler Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical class OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 239000012764 mineral filler Substances 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 230000005012 migration Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 229920006385 Geon Polymers 0.000 description 4
- 229920001944 Plastisol Polymers 0.000 description 4
- 239000004999 plastisol Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000003139 biocide Chemical class 0.000 description 3
- CMCJNODIWQEOAI-UHFFFAOYSA-N bis(2-butoxyethyl)phthalate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1C(=O)OCCOCCCC CMCJNODIWQEOAI-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229920003314 Elvaloy® Polymers 0.000 description 2
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 101100404567 Drosophila melanogaster nesd gene Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920006328 Styrofoam Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- -1 for example Polymers 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A roofing membrane and a polymer composition useful as a membrane includes (a) a polyvinyl chloride resin; (b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, a phthalate plasticizer for (a). The ratio of plasticizers (b) to (c), is from about 1.5 to 2.5:1 by weight. A method according to the invention includes coating a membrane as above onto a fabric backing material.
A roofing membrane and a polymer composition useful as a membrane includes (a) a polyvinyl chloride resin; (b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, a phthalate plasticizer for (a). The ratio of plasticizers (b) to (c), is from about 1.5 to 2.5:1 by weight. A method according to the invention includes coating a membrane as above onto a fabric backing material.
Description
20~9104 POLYVINYL CHLORIDE MEMlBRANE COMPOSlTION
AND METHOD FOR MAKING A
POLYVINYL CHLORIDE MEMBRANE
TECHNICAL FIELD
This invention generally relates to polyvinyl chloride compositions. More particularly, the present invention relates to po~yvinyl chloride compositions useful for l0 making a membrane. Specifically, the present invention relates to polyvinyl chloride membrane compositions having a unique plasticizer system which substantially prevents migration of the plasticizers from the membrane.
BACKGROUND OF THE INVENTION
lS It is known in the art to provide roofing membranes formed from a polyvinylchloride (hereinafter "PVC") resin composition. It is also known that the PVC resin should be plasticized in order to render it flexible for its intended purpose. It has been found that commonly used liquid plasticizers in PVC roofing membrane compositions will often migrate from the PVC and into adjacent material layers, such as insulation, 20 backing, coatings or the like. Furthermore, the plasticiær will often migrate to the surface of the membrane where it evaporates or is washed away by the weather. When the plasticiær migrates from the PVC composition, the membrane becomes stiff and is subject to shrinking and cracking.
In thepast, solutions to membrane shrinkage have included, for example, the 25 incorporation of highly elastic polyurethane as the main component in the membrane composition. Unfortunately, polyurethane in such an application is very expensive.
One example of forming a "dimensionally stable" i.e., s~ resistant PVC
membrane composition is disclosed in U.S. Pat. No. 4,358,499. The PVC membrane therein is formed by casting and gelling a plastisol layer, casting and gelling a second 30 plastisol layer thereon, and fusing the two layers. The plastisol includes PVC, a plasticizer such as a diaLkyl phtha1ate, an emulsifier, a filler, and heat, processing and UV stabilizers. It has been found, however, that without the complex plastisol casting method of the invention in that patent, PVC membrane compositions which include D-9108061 E~IR.P.US0067 . :: ' ~ . ' ' ' ' .
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AND METHOD FOR MAKING A
POLYVINYL CHLORIDE MEMBRANE
TECHNICAL FIELD
This invention generally relates to polyvinyl chloride compositions. More particularly, the present invention relates to po~yvinyl chloride compositions useful for l0 making a membrane. Specifically, the present invention relates to polyvinyl chloride membrane compositions having a unique plasticizer system which substantially prevents migration of the plasticizers from the membrane.
BACKGROUND OF THE INVENTION
lS It is known in the art to provide roofing membranes formed from a polyvinylchloride (hereinafter "PVC") resin composition. It is also known that the PVC resin should be plasticized in order to render it flexible for its intended purpose. It has been found that commonly used liquid plasticizers in PVC roofing membrane compositions will often migrate from the PVC and into adjacent material layers, such as insulation, 20 backing, coatings or the like. Furthermore, the plasticiær will often migrate to the surface of the membrane where it evaporates or is washed away by the weather. When the plasticiær migrates from the PVC composition, the membrane becomes stiff and is subject to shrinking and cracking.
In thepast, solutions to membrane shrinkage have included, for example, the 25 incorporation of highly elastic polyurethane as the main component in the membrane composition. Unfortunately, polyurethane in such an application is very expensive.
One example of forming a "dimensionally stable" i.e., s~ resistant PVC
membrane composition is disclosed in U.S. Pat. No. 4,358,499. The PVC membrane therein is formed by casting and gelling a plastisol layer, casting and gelling a second 30 plastisol layer thereon, and fusing the two layers. The plastisol includes PVC, a plasticizer such as a diaLkyl phtha1ate, an emulsifier, a filler, and heat, processing and UV stabilizers. It has been found, however, that without the complex plastisol casting method of the invention in that patent, PVC membrane compositions which include D-9108061 E~IR.P.US0067 . :: ' ~ . ' ' ' ' .
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plasticizers such as phthalate plasticizers, will result in membranes wherein the phthalate migrates out of the PVC, resulting in shrinkage and cracking of the membrane over periods of time.
However, phthalate plasticizers are known to effectively and efficiently 5 plasticize the PVC for roofing membrane applications. Therefore, a nesd exists for a phthalate plasticiæd PVC roofing membrane composition, which possesses an increased resistance to plasticizer migration from the PV~, and which is, therefore, resistant to shrinkage and cracking caused thereby. Also, a useful membrane composition should be highly resistant to ultraviolet light degradation and temperature fluctuation10 degradation.
j SUMMARY OF INVEN~ON
It is therefore, an object of the present invention to provide a plasticized polyvinyl chloride roofing membrane composition.
15It is another object of the present invention to provide a composition as above, which when employed to form a membrane, is resistant to migration of the plasticizers therein.
It is yet another object of the present invention to provide a roofing membrane which is resistant to shrinking and cracking.
20It is still another object to provide a roofing membrane which is highly resistant to ultraviolet light degradation.
It is yet another object to provide a roofing membrane which is resistant to heat degradation.
It is a further object of the present invention to provide a method for forming 25a roofing membrane.
It is a still further object of the present invention to provide a method for forming a roofing membrane which is resistant to shrinkage and weathering degradation.
At least one or more of the foregoing objects, together with the advantages thereof over the known art relating to roofing membranes and compositions therefor, 30which shall become apparent from the specification which follows, are accomplished by the invention as hereinafter described and claimed.
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plasticizers such as phthalate plasticizers, will result in membranes wherein the phthalate migrates out of the PVC, resulting in shrinkage and cracking of the membrane over periods of time.
However, phthalate plasticizers are known to effectively and efficiently 5 plasticize the PVC for roofing membrane applications. Therefore, a nesd exists for a phthalate plasticiæd PVC roofing membrane composition, which possesses an increased resistance to plasticizer migration from the PV~, and which is, therefore, resistant to shrinkage and cracking caused thereby. Also, a useful membrane composition should be highly resistant to ultraviolet light degradation and temperature fluctuation10 degradation.
j SUMMARY OF INVEN~ON
It is therefore, an object of the present invention to provide a plasticized polyvinyl chloride roofing membrane composition.
15It is another object of the present invention to provide a composition as above, which when employed to form a membrane, is resistant to migration of the plasticizers therein.
It is yet another object of the present invention to provide a roofing membrane which is resistant to shrinking and cracking.
20It is still another object to provide a roofing membrane which is highly resistant to ultraviolet light degradation.
It is yet another object to provide a roofing membrane which is resistant to heat degradation.
It is a further object of the present invention to provide a method for forming 25a roofing membrane.
It is a still further object of the present invention to provide a method for forming a roofing membrane which is resistant to shrinkage and weathering degradation.
At least one or more of the foregoing objects, together with the advantages thereof over the known art relating to roofing membranes and compositions therefor, 30which shall become apparent from the specification which follows, are accomplished by the invention as hereinafter described and claimed.
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In general, a polymer composition useful as a roofing membrane, according to the present invention comprises (a) a polyvinyl chloride resin; (b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and (c) a phthalate plasticizer for (a). The ratio of the plasticizers (b) to (c) is from about l.5 to 2.5:1.
There is also provided according to the present invention, a roofing membrane which comprises a first layer and a second layer. The first layer is formed from a polymer composition which comprises~-(a) a polyvinyl chloride resin; (b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a). The ratio of the plasticizers (b) to (c) is from about l.5 to 2.5:I by weight. The second layer comprises a fabric backing material.
A method of forming a roofing membrane comprises the step of forming a membrane composition. The membrane composition comprises (a) a polyvinyl chloride resin; (b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a). The ratio of plasticizers (b) to (c), is from about 1.5 to 2.5:1 by weight. The method alsa includes the step of coating the membrane composition onto a fabric backing material.
PREFERRED EMBODIMENT F~R CARRYING OUT-TIIE INVENIION
As will become apparent from the description which follows, the present invention provides a novel composition useful for forming a membrane, and a novel method for forming a roofing membrane. Membranes formed according to the presentinvention have increased resistance to,shrinking and cracking caused by plasticizer migration. The membranes a1so exhibit increased resistance to ultraviolet light and other weather induced degradation.
It has also been unexpectedly found, that compositions and membranes according to the present invention, have increased compatibility with polystyrene materials, such as Styrofoam brand insulation available from the Dow Chemical Company, and AMOCOR-PB4 protection board from AMOCO Foam Products.
The present invention is directed toward a polymeric membrane and a 30 composition therefor. While the invention is useful in any application wherein a membrane is re~uired, it has particular application to membranes used to provide Q~ FTR .P.TJ~S()()~i7 , . ~ . . :, . :
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There is also provided according to the present invention, a roofing membrane which comprises a first layer and a second layer. The first layer is formed from a polymer composition which comprises~-(a) a polyvinyl chloride resin; (b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a). The ratio of the plasticizers (b) to (c) is from about l.5 to 2.5:I by weight. The second layer comprises a fabric backing material.
A method of forming a roofing membrane comprises the step of forming a membrane composition. The membrane composition comprises (a) a polyvinyl chloride resin; (b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a). The ratio of plasticizers (b) to (c), is from about 1.5 to 2.5:1 by weight. The method alsa includes the step of coating the membrane composition onto a fabric backing material.
PREFERRED EMBODIMENT F~R CARRYING OUT-TIIE INVENIION
As will become apparent from the description which follows, the present invention provides a novel composition useful for forming a membrane, and a novel method for forming a roofing membrane. Membranes formed according to the presentinvention have increased resistance to,shrinking and cracking caused by plasticizer migration. The membranes a1so exhibit increased resistance to ultraviolet light and other weather induced degradation.
It has also been unexpectedly found, that compositions and membranes according to the present invention, have increased compatibility with polystyrene materials, such as Styrofoam brand insulation available from the Dow Chemical Company, and AMOCOR-PB4 protection board from AMOCO Foam Products.
The present invention is directed toward a polymeric membrane and a 30 composition therefor. While the invention is useful in any application wherein a membrane is re~uired, it has particular application to membranes used to provide Q~ FTR .P.TJ~S()()~i7 , . ~ . . :, . :
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weathering protection to roofs or the like. Hence, while all membrane applications are within the scope of the invention, the present disclosure will make reference to roofing applications for exemplary purposes only.
Similarly, the present invention has application to a variety of membrane 5 composition polymers. However, PVC resin is the preferred membrane polymer. Anexample of a useful PVC resin is Geon 30 available from B.F. Goodrich. Other PVCresins may also be useful, as will be apparent ~om the discussion to follow.
As noted hereinabove, when properly plasticized, PVC possesses excellent membrane forming characteristics, such as structural integrity and weather resistance.
10 The drawback heretofore has been in regard to the migration of the plasticizer from the PVC after a period of time.
According to the present invention, the PVC resin is plasticized with a phthalate type, liquid plasticizer, such as Palatinol 711P from BASF Wyandotte Corp.
of Parsippany, New Jersey. Palatinol 711P is known to be based upon C7 to Cll 15 alcohols. Liquid phthalate plasticizers are known to effectively plasticize PVC resins in a manner suitable for membrane applications. Other useful phthalate plasticizer include diisodecylphthalate types.
- The composition of the present invention also includes a carbon monoxide/ethylenelvinyl acetate terpolymer plasticizer for the PVC resin. An example 20 of such a terpolymer is Elvaloy 741 from DuPont, which has a molecular weight greater than about 250,000. It has been found, that when the terpolymer is employed in a ratio with the phthalate plasticizer, of from about 1.5 to 2.5:1 to 1, and more preferably at a ratio of about 2:1, the resulting plasticized PVC composition shows improved resistance to plasticizer migration. As will be further exemplified hereinbelow,25 membranes formed from such a composition uill possess resistance to shrinkage and cracking.
When employing a PVC resin such as Geon 30, which is known to have a molecular weight of about 65,000 and an inherent viscosity of 1.02 according to ASTM
D1243, the composition preferably includes from about 30 to about 60 parts by weight 30 of the carbon monoxide/ethylenelvinyl acetate terpolymer, per 100 parts by weight of PVC resin (hereinafter referred to às "phrn). Furthermore, the composition preferably T~TT~ Tl TT~ 0/;7 .. . . . .
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includes from about 15 to about 30 phr of the phthalate plasticiær. As will be appreciated by one skilled in the membrane art, when a PVC resin having a different molecular weight is employed, which resin would have a different inherent viscosity, different amounts of the two types of plasticiærs might be employed in order to provide 5 a suitably plasticiæd composition. Such amounts might also vary depending upon the nature of the membrane to be formed. All sueh compositions, having the plasticiær amounts in the prescribed ratios, are within the~scope of the present invention.The carbon monoxide/ethylene/vinyl acetate terpolymer is less stable when exposed to ultraviolet (hereinafter referred to as "UVn) light radiation than most PVC
10 resins. Hence, it has been found that compositions according to the present invention may be provided with UV-protecting filler or pigments. As an example, a useful composition according to the present invention, employing a PVC resin such as Geon 30, includes from about 15 to about 25 phr of titanium dioxide. This provides unexpectedly high UV protection for membranes according to the present invention.
Compositions according to the invention may also contain other conventional additives, such as processing aids or the like. For example, the compositions may include other fillers such as calcium carbonate; heat stabiliærs such as barium/zinc;
lubricants such as stearic acid; acid acceptors such as epoxidized soybean oil; other W-protectors such as substituted hydroxyphenyl benzotriazole; antioxidants; biocides; anti-20 slipping agents; and the like.
An exemplary formulation according to the present invention is listed in Table I hereinbelow.
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TABLE I
EXEMPLARY FORMULATION
Component Amounta Geon 30b 100 Plasticizer for Polyvinyl ChlorideC 45 Titanium Dioxide ~ 25 Phthalate Plasticizerd 20 Calcium Carbonate Filler 10 Epoxidized Soybean Oil S
Barium/Zinc Heat Stabilizere 3 Stearic Acid 0.5 UV Stabilizerf 0.5 Antioxidant 0.5 Biocide 1.5 Kemamide Eg 0.2 Advawax 280h 0.1 a) parts per 100 parts of the polyvinyl chloride component 20 b) polyvinyl chloride from BF Goodrich c) such as a carbon monoxide/ethylene/vinyl acetate terpolymer, for example, Elvaloy 741 from DuPont d) Palatinol 711 P from BASF
e) Mark 4737 from Witco Chemical Corp., New York 25 f) Tinuvin 622 from Ciba-Geigy, a substituted hydroxyphenyl benzotrazole g) anti-slip agent from Witco Chemical Corp., New York h) anti-blocking agent from Carlisle Chemical Works, Brunswick, New Jersey n-s1nRn~1 ~71R.P.USO067 , . .: :, -~, . - .
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While it is understood that other additives such as processing aids are optional, and that amounts of each component may vary with the type of PVC resinemployed, Table II lists exemplary useful ranges of each component, if employed. It is also understood that the actual components listed are examples of numerous such 5 components useful in the practice of the present invention, and that amounts of the components may vary other than as listed hereinbelow, depending upon the actual component employed.
TABLE II
COMPOSITION RANGES
Componenti PHR RangeJ
Polyvinyl Chloride 100 Plasticizer for Polyvinyl Chloride 30 - 60 Titanium Dioxide15 - 25 Phthalate Plasticizer 15 - 30 Calcium Carbonate FiUer 0 - 15 Epoxidized Soybean Oil 4 - 6 Barium/Zinc Heat Stabilizer 2 - 4 Stearic Acid 0.25 - 1.0 UV Stabilizer0.2 - 0.6 Antioxidant 0.2 - 0.6 Biocide 1 - 2 Anti-Slip Agent0.2 - 0.4 AntiblockAgent0.1 - 0.2 i) for an explanation of components, see Table I
j) parts per 100 parts of the polyvinyl chloride component n ol~Q~;l FIR.P.IJ~-)067 20~910~
As noted hereinabove, the compositions according to the present invention are useful for forming membranes such as for roofing applications or the like. Any method known in the art for forming membranes or sheeting from plasticized polymer ,- compositions is considered to be within the scope of the present invention.
5For example, the component ingredients can be admixed, utilizing an internal mixer (such as a Banbury mixer), an extruder, and/or a two-roll mill, or other mixer suitable for forming a viscous relatively unifor~ admixture. The resulting admixture is then sheeted to thicknesses ranging preferably from about 5 to 200 mils, and more preferably from about 35 to 100 mils, by conventional sheeting methods, for example, 10milling, calendaring, or extrusion. The sheeting can be cut to desired length and width dimensions at this time.
The present invention has particular application to multi-ply roofing membranes which include a first layer formed from a composition as discussed hereinabove, coated onto a backing layer such as a fabric material. A second layer of 15a membrane according to the present invention may be bonded to the fabric backing material, such that the fabric backing material is sandwiched between two layers of the invention composition.
Preferably, the fabric backing or reinforcing material is a "mesh" type material, such as 62006 from Highland Industries, Inc., of Westwood, New Jersey.20This material is fabricated from a yarn made from polyester filaments, at 1000 denier.
General Experimental In order to demonstrate the effectiveness of the present invention in 25accomplishing the objectives thereof, a composition according to the present invention, and containing the ingredients as in Table I listed hereinabove, was tested employing a QW Weatherometer, as manufactured by Q-Panel. The device was run at 70C using UVB-313 bulbs for 8 hrs/50C condensate for four hours, repetitive for 5,000 hours of total exposure. For comparison, similar Weatherometer tests were conducted upon 30commerciatly available roofing membranes including UltraPly 78+ available from the Assignee of record; Fibretite available from Seaman Corp., Sarasota, Florida; Sarnafil n ~1n~n,c1 F~R.P.US0067 .
2 ~
available from Sarnafil, Inc., Canton, Massachusetts; Trocal SR-60 available from Huls America, Piscataway, New Jersey; and, Genflex available from Gencorp Polymer Products, Toledo, Ohio.
The Weatherometer tests simulated weather conditions and specificaUy, S ultraviolet exposure for the various membranes. The membranes were then examined under magnification for cracking therein. The results of the experiments are listed in Table III hereinbelow.
TABLE m WEATHERING TEST
Membrane Result Inventionk No cracks visible UltraPly 78+ No cracks visible Fibretite Cracks visiblel Sarnafil Cracks visiblem Trocal SR-60 Cracks visiblem Genflex Cracks visiblem 20 k) a composition according to Table I hereinabove 1) at 30 power magnification - . m) at 7 power magnification n-010~ 1 FIR.P.US006'7 ~ol9o9lo~
Thus, it has been shown, that the composition according to the present invention performs as well as the best performing commercial membrane evaluated in this weathering test, and is therefore, clearly useful in forming a membrane composition which is resistant to migration of the plasticizers therein. The membrane is useful, as 5 for example, a roofing membrane, because of its particular resistance to shrinking and cracking, when compared to other commercially avai1able membranes. Also, the present invention has greater resistance to ~IJV induced degradation than many commercially used membrane compositions.
The tests performed herein are for exemplary purposes only and do not 10 necessary limit the scope of the present invention. Furthermore, it is to be understood that the invention is not limited to these specific polyvinyl chloride resins, terpolymers, or phthalate plasticizers as noted hereinabove. Furthermore, the composition according to the present invention may comprise various other additives and processing aids without departing from the scope of the invention. Those skilled in the art may readily 15 select other polymers, plasticizers, and the like according to the disclosure made hereinabove. Similarly, the invention is not necessarily limited to the particular methods of forming a membrane as exemplified hereinabove.
Thus, it is believed that any of the variable disclosed herein can readily be determined and controlled without departing from the scope of the invention herein 20 disclosed and described. Moreover, the scope of the invention shall include all modifications and variations that fall within the scope of the attached claims.
n a~ il FTR.P.~J~ i7
Similarly, the present invention has application to a variety of membrane 5 composition polymers. However, PVC resin is the preferred membrane polymer. Anexample of a useful PVC resin is Geon 30 available from B.F. Goodrich. Other PVCresins may also be useful, as will be apparent ~om the discussion to follow.
As noted hereinabove, when properly plasticized, PVC possesses excellent membrane forming characteristics, such as structural integrity and weather resistance.
10 The drawback heretofore has been in regard to the migration of the plasticizer from the PVC after a period of time.
According to the present invention, the PVC resin is plasticized with a phthalate type, liquid plasticizer, such as Palatinol 711P from BASF Wyandotte Corp.
of Parsippany, New Jersey. Palatinol 711P is known to be based upon C7 to Cll 15 alcohols. Liquid phthalate plasticizers are known to effectively plasticize PVC resins in a manner suitable for membrane applications. Other useful phthalate plasticizer include diisodecylphthalate types.
- The composition of the present invention also includes a carbon monoxide/ethylenelvinyl acetate terpolymer plasticizer for the PVC resin. An example 20 of such a terpolymer is Elvaloy 741 from DuPont, which has a molecular weight greater than about 250,000. It has been found, that when the terpolymer is employed in a ratio with the phthalate plasticizer, of from about 1.5 to 2.5:1 to 1, and more preferably at a ratio of about 2:1, the resulting plasticized PVC composition shows improved resistance to plasticizer migration. As will be further exemplified hereinbelow,25 membranes formed from such a composition uill possess resistance to shrinkage and cracking.
When employing a PVC resin such as Geon 30, which is known to have a molecular weight of about 65,000 and an inherent viscosity of 1.02 according to ASTM
D1243, the composition preferably includes from about 30 to about 60 parts by weight 30 of the carbon monoxide/ethylenelvinyl acetate terpolymer, per 100 parts by weight of PVC resin (hereinafter referred to às "phrn). Furthermore, the composition preferably T~TT~ Tl TT~ 0/;7 .. . . . .
.
, " ~ .
.
2~9~0~
includes from about 15 to about 30 phr of the phthalate plasticiær. As will be appreciated by one skilled in the membrane art, when a PVC resin having a different molecular weight is employed, which resin would have a different inherent viscosity, different amounts of the two types of plasticiærs might be employed in order to provide 5 a suitably plasticiæd composition. Such amounts might also vary depending upon the nature of the membrane to be formed. All sueh compositions, having the plasticiær amounts in the prescribed ratios, are within the~scope of the present invention.The carbon monoxide/ethylene/vinyl acetate terpolymer is less stable when exposed to ultraviolet (hereinafter referred to as "UVn) light radiation than most PVC
10 resins. Hence, it has been found that compositions according to the present invention may be provided with UV-protecting filler or pigments. As an example, a useful composition according to the present invention, employing a PVC resin such as Geon 30, includes from about 15 to about 25 phr of titanium dioxide. This provides unexpectedly high UV protection for membranes according to the present invention.
Compositions according to the invention may also contain other conventional additives, such as processing aids or the like. For example, the compositions may include other fillers such as calcium carbonate; heat stabiliærs such as barium/zinc;
lubricants such as stearic acid; acid acceptors such as epoxidized soybean oil; other W-protectors such as substituted hydroxyphenyl benzotriazole; antioxidants; biocides; anti-20 slipping agents; and the like.
An exemplary formulation according to the present invention is listed in Table I hereinbelow.
1-) 41n~n~1 FTR.P.US0067 - ~
-. - ' ~
~0~910~
TABLE I
EXEMPLARY FORMULATION
Component Amounta Geon 30b 100 Plasticizer for Polyvinyl ChlorideC 45 Titanium Dioxide ~ 25 Phthalate Plasticizerd 20 Calcium Carbonate Filler 10 Epoxidized Soybean Oil S
Barium/Zinc Heat Stabilizere 3 Stearic Acid 0.5 UV Stabilizerf 0.5 Antioxidant 0.5 Biocide 1.5 Kemamide Eg 0.2 Advawax 280h 0.1 a) parts per 100 parts of the polyvinyl chloride component 20 b) polyvinyl chloride from BF Goodrich c) such as a carbon monoxide/ethylene/vinyl acetate terpolymer, for example, Elvaloy 741 from DuPont d) Palatinol 711 P from BASF
e) Mark 4737 from Witco Chemical Corp., New York 25 f) Tinuvin 622 from Ciba-Geigy, a substituted hydroxyphenyl benzotrazole g) anti-slip agent from Witco Chemical Corp., New York h) anti-blocking agent from Carlisle Chemical Works, Brunswick, New Jersey n-s1nRn~1 ~71R.P.USO067 , . .: :, -~, . - .
.' 1 0 ~
While it is understood that other additives such as processing aids are optional, and that amounts of each component may vary with the type of PVC resinemployed, Table II lists exemplary useful ranges of each component, if employed. It is also understood that the actual components listed are examples of numerous such 5 components useful in the practice of the present invention, and that amounts of the components may vary other than as listed hereinbelow, depending upon the actual component employed.
TABLE II
COMPOSITION RANGES
Componenti PHR RangeJ
Polyvinyl Chloride 100 Plasticizer for Polyvinyl Chloride 30 - 60 Titanium Dioxide15 - 25 Phthalate Plasticizer 15 - 30 Calcium Carbonate FiUer 0 - 15 Epoxidized Soybean Oil 4 - 6 Barium/Zinc Heat Stabilizer 2 - 4 Stearic Acid 0.25 - 1.0 UV Stabilizer0.2 - 0.6 Antioxidant 0.2 - 0.6 Biocide 1 - 2 Anti-Slip Agent0.2 - 0.4 AntiblockAgent0.1 - 0.2 i) for an explanation of components, see Table I
j) parts per 100 parts of the polyvinyl chloride component n ol~Q~;l FIR.P.IJ~-)067 20~910~
As noted hereinabove, the compositions according to the present invention are useful for forming membranes such as for roofing applications or the like. Any method known in the art for forming membranes or sheeting from plasticized polymer ,- compositions is considered to be within the scope of the present invention.
5For example, the component ingredients can be admixed, utilizing an internal mixer (such as a Banbury mixer), an extruder, and/or a two-roll mill, or other mixer suitable for forming a viscous relatively unifor~ admixture. The resulting admixture is then sheeted to thicknesses ranging preferably from about 5 to 200 mils, and more preferably from about 35 to 100 mils, by conventional sheeting methods, for example, 10milling, calendaring, or extrusion. The sheeting can be cut to desired length and width dimensions at this time.
The present invention has particular application to multi-ply roofing membranes which include a first layer formed from a composition as discussed hereinabove, coated onto a backing layer such as a fabric material. A second layer of 15a membrane according to the present invention may be bonded to the fabric backing material, such that the fabric backing material is sandwiched between two layers of the invention composition.
Preferably, the fabric backing or reinforcing material is a "mesh" type material, such as 62006 from Highland Industries, Inc., of Westwood, New Jersey.20This material is fabricated from a yarn made from polyester filaments, at 1000 denier.
General Experimental In order to demonstrate the effectiveness of the present invention in 25accomplishing the objectives thereof, a composition according to the present invention, and containing the ingredients as in Table I listed hereinabove, was tested employing a QW Weatherometer, as manufactured by Q-Panel. The device was run at 70C using UVB-313 bulbs for 8 hrs/50C condensate for four hours, repetitive for 5,000 hours of total exposure. For comparison, similar Weatherometer tests were conducted upon 30commerciatly available roofing membranes including UltraPly 78+ available from the Assignee of record; Fibretite available from Seaman Corp., Sarasota, Florida; Sarnafil n ~1n~n,c1 F~R.P.US0067 .
2 ~
available from Sarnafil, Inc., Canton, Massachusetts; Trocal SR-60 available from Huls America, Piscataway, New Jersey; and, Genflex available from Gencorp Polymer Products, Toledo, Ohio.
The Weatherometer tests simulated weather conditions and specificaUy, S ultraviolet exposure for the various membranes. The membranes were then examined under magnification for cracking therein. The results of the experiments are listed in Table III hereinbelow.
TABLE m WEATHERING TEST
Membrane Result Inventionk No cracks visible UltraPly 78+ No cracks visible Fibretite Cracks visiblel Sarnafil Cracks visiblem Trocal SR-60 Cracks visiblem Genflex Cracks visiblem 20 k) a composition according to Table I hereinabove 1) at 30 power magnification - . m) at 7 power magnification n-010~ 1 FIR.P.US006'7 ~ol9o9lo~
Thus, it has been shown, that the composition according to the present invention performs as well as the best performing commercial membrane evaluated in this weathering test, and is therefore, clearly useful in forming a membrane composition which is resistant to migration of the plasticizers therein. The membrane is useful, as 5 for example, a roofing membrane, because of its particular resistance to shrinking and cracking, when compared to other commercially avai1able membranes. Also, the present invention has greater resistance to ~IJV induced degradation than many commercially used membrane compositions.
The tests performed herein are for exemplary purposes only and do not 10 necessary limit the scope of the present invention. Furthermore, it is to be understood that the invention is not limited to these specific polyvinyl chloride resins, terpolymers, or phthalate plasticizers as noted hereinabove. Furthermore, the composition according to the present invention may comprise various other additives and processing aids without departing from the scope of the invention. Those skilled in the art may readily 15 select other polymers, plasticizers, and the like according to the disclosure made hereinabove. Similarly, the invention is not necessarily limited to the particular methods of forming a membrane as exemplified hereinabove.
Thus, it is believed that any of the variable disclosed herein can readily be determined and controlled without departing from the scope of the invention herein 20 disclosed and described. Moreover, the scope of the invention shall include all modifications and variations that fall within the scope of the attached claims.
n a~ il FTR.P.~J~ i7
Claims (15)
1. A polymer composition useful as a membrane comprising:
(a) a polyvinyl chloride resin;
(b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a);
and, (c) a phthalate plasticizer for (a);
wherein the ratio of said plasticizers (b) to (c), is from about 1.5 to 2.5:1 byweight.
(a) a polyvinyl chloride resin;
(b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a);
and, (c) a phthalate plasticizer for (a);
wherein the ratio of said plasticizers (b) to (c), is from about 1.5 to 2.5:1 byweight.
2. A polymer composition, as set forth in claim, comprising 100 parts by weight of said polyvinyl chloride resin; from about 30 to about 60 parts by weight of saidcarbon monoxide/ethylene/vinyl acetate terpolymer plasticizer; and, from about 15 to about 30 parts by weight of said phthalate plasticizer.
3. A polymer composition, as set forth in claim 2, comprising 45 parts by weight of said carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer; and, 20 parts by weight of said phthalate plasticizer.
4. A polymer composition, as set forth in claim 1, useful as a roofing membrane,further comprising at least one additive of an ultraviolet light-protecting filler.
5. A polymer composition, as set forth in claim 4, wherein the composition comprises as an ultraviolet light-protecting filler, from about 15 to about 25 parts by weight of titanium dioxide, per 100 parts by weight of said polyvinyl chloride resin.
6. A polymer composition, as set forth in claim 4, wherein the composition further comprises a mineral filler, in the range of from about 0 to about 15 parts by weight of calcium carbonate, per 100 parts by weight of said polyvinyl chloride resin.
7. A polymer composition, as set forth in claim 4, wherein the composition comprises as an organochemical acid acceptor, in the range of from about 4.0 to about 6.0 parts by weight of epoxidized soybean oil per 100 parts by weight of said polyvinyl chloride resin.
8. A polymer composition, as set forth in claim 4, wherein the composition further comprises from about 2 to about 4 parts 4, weight of a heat stabilizer, per 100 parts by weight of said polyvinyl chloride resin.
9. A polymer composition, as set forth in claim 4, wherein the composition comprises as a processing aid, from about 0.25 to about 1.0 parts by weight of stearic acid per 100 parts of said polyvinyl chloride resin.
10. A polymer composition, as set forth in claim 4, wherein the composition comprises as an ultraviolet light-protecting filler, from about 0.2 to about 0.6 parts by weight of a substituted hydroxyphenyl benzotriazole per 100 parts by weight of said polyvinyl chloride resin.
11. A membrane comprising:
a first layer and a second layer;
said first layer formed from a polymer composition comprising (a) a polyvinyl chloride resin;
(b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a);
wherein the ratio of said plasticizers (b) to (e), is from about 1.5 to 2.5:1 by weight; and, said second layer comprises a fabric backing material.
a first layer and a second layer;
said first layer formed from a polymer composition comprising (a) a polyvinyl chloride resin;
(b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a);
wherein the ratio of said plasticizers (b) to (e), is from about 1.5 to 2.5:1 by weight; and, said second layer comprises a fabric backing material.
12. A membrane as set forth in claim 11, useful as a roofing membrane, further comprising an ultraviolet light-protecting filler.
13. A method of forming a membrane comprising the steps of:
forming a membrane composition comprising:
(a) a polyvinyl chloride resin;
(b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a);
wherein the ratio of said plasticizers (b) to (c), is from about 1.5 to 2.5:1 by weight; and, coating said membrane composition onto a fabric backing material.
forming a membrane composition comprising:
(a) a polyvinyl chloride resin;
(b) a carbon monoxide/ethylene/vinyl acetate terpolymer plasticizer for (a); and, (c) a phthalate plasticizer for (a);
wherein the ratio of said plasticizers (b) to (c), is from about 1.5 to 2.5:1 by weight; and, coating said membrane composition onto a fabric backing material.
14. A method as set forth in claim 12, wherein a second membrane is coated onto said fabric backing material.
15. A method as set forth in claim 13, useful for forming a roofing membrane, wherein said membrane composition further comprises an ultraviolet light-protecting filler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90340492A | 1992-06-24 | 1992-06-24 | |
| US903,404 | 1992-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2099104A1 true CA2099104A1 (en) | 1993-12-25 |
Family
ID=25417448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2099104 Abandoned CA2099104A1 (en) | 1992-06-24 | 1993-06-23 | Polyvinyl chloride membrane composition and method for making a polyvinyl chloride membrane |
Country Status (2)
| Country | Link |
|---|---|
| BR (1) | BR9302452A (en) |
| CA (1) | CA2099104A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025763A1 (en) * | 1996-12-09 | 1998-06-18 | Minnesota Mining And Manufacturing Company | Uv protected syndiotactic polystyrene overlay films |
| US6977277B2 (en) * | 2000-07-18 | 2005-12-20 | Exxonmobil Research And Engineering Company | Polyvinyl chloride resins |
| WO2007030151A1 (en) * | 2005-09-02 | 2007-03-15 | P & G Solutions, Inc. | Weatherable corrosion-resistant flashing |
| CN109422976A (en) * | 2017-08-25 | 2019-03-05 | 于银强 | A kind of anti-fouling and self-cleaning type canopy material |
| US10731057B2 (en) | 2017-06-02 | 2020-08-04 | Carlisle Intangible, LLC | Pressure-sensitive PVC cover strip |
| EP3752669A4 (en) * | 2018-02-12 | 2021-12-01 | Omnova Solutions Inc | Discoloration resistant fabric |
-
1993
- 1993-06-23 CA CA 2099104 patent/CA2099104A1/en not_active Abandoned
- 1993-06-23 BR BR9302452A patent/BR9302452A/en not_active Application Discontinuation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025763A1 (en) * | 1996-12-09 | 1998-06-18 | Minnesota Mining And Manufacturing Company | Uv protected syndiotactic polystyrene overlay films |
| US5981076A (en) * | 1996-12-09 | 1999-11-09 | 3M Innovative Properties Company | UV protected syndiotactic polystyrene overlay films |
| US6120901A (en) * | 1996-12-09 | 2000-09-19 | 3M Innovative Properties Company | UV protected syndiotactic polystyrene overlay films |
| US6977277B2 (en) * | 2000-07-18 | 2005-12-20 | Exxonmobil Research And Engineering Company | Polyvinyl chloride resins |
| WO2007030151A1 (en) * | 2005-09-02 | 2007-03-15 | P & G Solutions, Inc. | Weatherable corrosion-resistant flashing |
| US10731057B2 (en) | 2017-06-02 | 2020-08-04 | Carlisle Intangible, LLC | Pressure-sensitive PVC cover strip |
| CN109422976A (en) * | 2017-08-25 | 2019-03-05 | 于银强 | A kind of anti-fouling and self-cleaning type canopy material |
| EP3752669A4 (en) * | 2018-02-12 | 2021-12-01 | Omnova Solutions Inc | Discoloration resistant fabric |
| US12226991B2 (en) | 2018-02-12 | 2025-02-18 | Surteco North America, Inc. | Discoloration resistant fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9302452A (en) | 1994-01-11 |
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