GB2445854A - Hydrophilic polymer substrates - Google Patents
Hydrophilic polymer substrates Download PDFInfo
- Publication number
- GB2445854A GB2445854A GB0800648A GB0800648A GB2445854A GB 2445854 A GB2445854 A GB 2445854A GB 0800648 A GB0800648 A GB 0800648A GB 0800648 A GB0800648 A GB 0800648A GB 2445854 A GB2445854 A GB 2445854A
- Authority
- GB
- United Kingdom
- Prior art keywords
- substrate
- hydrophilic
- sulfonation
- polymer
- layer
- 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.)
- Withdrawn
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 45
- 229920001477 hydrophilic polymer Polymers 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 43
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 13
- 239000004417 polycarbonate Substances 0.000 claims abstract description 13
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 238000006277 sulfonation reaction Methods 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 24
- 230000000845 anti-microbial effect Effects 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 230000006872 improvement Effects 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- -1 triethylainine Chemical compound 0.000 claims description 6
- 229920006163 vinyl copolymer Polymers 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001990 intravenous administration Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 150000000994 L-ascorbates Chemical class 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- PUYZMNHGDGPRCS-UHFFFAOYSA-N [chlorosulfonyl(dimethyl)silyl]methane Chemical compound C[Si](C)(C)S(Cl)(=O)=O PUYZMNHGDGPRCS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 25
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 11
- 230000000007 visual effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 241001669573 Galeorhinus galeus Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
A method for the preparation of a polymer substrate e.g. polycarbonate, comprises; treating the substrate with SO3 to form a hydrophilic layer, and eliminating contact of the substrate with the sulphur trioxide once the hydrophilic layer has formed. Residual sulphonic acid groups may be neutralised by contacting the substrate with a base. The SO3 can be either liquid or gaseous and can be produced by the oxidation of SO2 in the presence of a catalyst and/or UV radiation. The SO3 may be added in a dry atmosphere in a concentration of 0.5-20 % by volume for a period of 5 seconds - 30 minutes if gaseous or 1 second to 10 minutes if liquid. The sulphonation process can be aided using heat or UV radiation. Prior to contact with the SO3 the polymer substrate may be exposed to organic solvents. A hydrophilic substrate layer is also disclosed, which comprises a polar functional group, especially a sulphonic group, bonded to the polymer.
Description
METHOD OF SULFONATION OF POLYMER SUBSTRATE TO IMPART A
HYDROPHIUC LAYER IN SAID SUBSTRATE WITH IMPROVEMENT IN AT
LEAST ONE OF ANTI-FOG, ANTI-STATIC, WETTABILITY, LUBRICITY AND ANTI-MICROBIAL PROPERTIES, AND ARTiCLES MADE THEREBY This Application claims the benefit of U.S. Provisional Application Serial No. 60/885,O9lfiled January 16, 2007, and U.S. Utility Patent Application Serial No. 11/748,252 filed May 142007, which are both incorporated herein in their entirety.
The present invention is directed to a method for sulfonating polymer substrates to impart a hydrophilic layer in said substrate to impart improvement in at least one of anti-fogging, anti-static, wettability, lubricity and/or anti-microbial properties.
The present invention is further directed to polymer substrates having a hydrophilic layer obtained by sulfonation to impart improvement in at least one of anti-fogging, anti-static, wettability, lubricity and/or anti-microbial properties of such polymer substrates.
The present invention yet further relates to a method of sulfonating clear polymer substrates to impart a hydrophilic layer in said substrate exhibiting improved at least one ofanti-lbgging, anti-static, wettability, lubricityand/or anti-microbial properties without substantially affecting the transparency of said treated polymer substrate.
The present invention further relates to articles made from clear polymer substrates treated with a sulfonation process to impart a hydrophilic layer in said substrate that imparts improvement in at least one of anti-fogging, anti-static, wettabiity, lubricity and/or anti-microbial properties without substantially affecting the transparency of said articles.
Polymer substrates and articles made therefrom commonly exhibit static and fogging properties that affect their usefulness in many applications to which they are used. In addition, under certain conditions, the lubricity and anti-microbial properties of polymers used for medical and packaging uses can be improved to increase their usefulness in medical and packaging fields. Moreover, wettability becomes an issue for many applications and has an effect on many of the properties of the polymer. For example, the phenomenon commonly called fogging is observed widely in various applications of transparent polymer films or sheets. The term fogging describes the condensation of water vapor from air, in the form of discrete water droplets, on a polymer surface. In such situations, light transmitted through polymers that suffer from "fogging" is scattered by the water droplets accumulated on the surface of the polymer, causing the view to be hindered. Polymers are generally non- polar compounds that repel water to a certain degree, according to their surface tension. When affinity of the condensate for the substrate is high, the contact angles between the droplets and the substrate surface are low and very little lbgging occurs. In addition, two other key factors influencing the fogging phenomenon are the level of moisture in the air and the difference in temperature between the air and the polymer part. One route that has been widely used to help minimize fogging is improving the wetting performances of the polymer. Wettable surfaces allow liquid films to form at their surfaces instead of droplets. In this case, the contact angles are very low and the transmittance of light and formation of images are not prevented, Typical anti-fogging additives contain molecules composed of both a hydrophilic part that is attracted by water, and a long hydrophobic part, such as a lipophilic part, adapted to the polymer substrate, such as esters of fatty esters. Another common method employed in combatting fogging is through temporary or permanent coatings. While it has been known that polymers can be sulfonated to have increased anti-static properties, there have been no studies of using sulfonation to obtain anti-fog, wettable transparent layers that have improved anti-static, anti-fogging, anti-microbial, improved wettability and improved lubricity. Moreover, when polymers, in the form of powders, are used in paints or other mixtures they must exhibit some degree of wettability in order to be useful. In some applications such as paints and retarding additives for cements, polymer powders are added and then a substantial amount of surfactant must be added to permit the polymers to be sufficiently wetted to form a useful composition. The improved wettability of the sulfonated powders in the present invention substantially reduces the amount of surfactant in such compositions to impart the same or improved properties.
Patchen, U.S. Patent No. 6,923,997 discloses anti-fogging compositions and methods of using the same. Various compositions for food packaging uses are disclosed.
For example, one composition of the anti-fogging composition is (i) a nonionic surfactant blend comprising a fatty acid ester and an ethoxylated compound and (ii) acetone.
Another example is an anti-fogging nonionic surctant blend comprising a fatty acid ester and an ethoxylated compound and (ii) a solvent selected from methyl acetate, isopropyl alcohol, ethanol, and mixtures thereof. The method of defogging the food packaging surface entails selecting a surfactant, providing (I) an anti-fogging nonionic surfactant blend comprising a fatty ester and an ethoxylated compound and applying the anti-fogging composition to the surface. Another method disclosed comprises selecting a surface, providing an anti-fogging nonionic surfactant blend comprising a fatty acid ester and an ethoxylated compound and (ii) a solvent selected from methyl acetate, isopropyl alcohol, ethanol, and mixtures thereof to fomi an anti-fogging composition, and applying the anti-fogging composition to the surface.
Bates, U.S. Patent No. 6,706,389discloses a packaging film that includes a heat sealable layer coated with one or more anti-fogging agents disposed on a binder; an anti-blocking agent, and no more than about 800 ppm slip agent. The heat sealable layer includes a polymer that includes mer units derived from ethylene while the binder includes a polymer that includes mer units derived from an ester of(meth)acrylic acid and/or vinyl acetate mers. The anti-blocking agent can be in any layer of the film where it provides the desired anti-fogging effect. Such a film, as well as packaging made therefrom, can be used to package a variety of products, having particular utility with respect to most products.
Dixon, U.S. Patent No. 2,272,831 discloses a sulfonation of clearpolystyrene to impart anti-static properties to a surface of a treated substrate without substantially affecting the surface appearance and transparency of the polystyrene substrate. The sulfonation occurs by the exposure of the surface of a polystyrene substrate to concentrated sulfuric acid solutions.
Wailes, U.S. Patent No. 3,959,561 discloses a method for the rapid rendering of transparent polymer articles astatic by treating the articles with gaseous sulfur trioxide (SO3) followed by treatment with a base such as ammonia and water or dilute aqueous ammonia. The articles are rendered pennanently astatic without affecting their Iransparency.
It is thereibre desirable to provide an improved polymer substrate and method of producing such substrate which addresses problems and/or which more generally offers improvements or an alternative to existhig arrangements.
According to the present invention there is therefore provided a method for the preparation of a polymer substrate, and a polymer substrate prepared by the method, as described in the accompanying claims. There is also provided a polymer substrate as further described in the accompanying claims.
In an embodiment of one aspect of the invention there is provided a method for the preparation of a polymer substrate with at least one of improved anti-fogging, anti-static, wettability, lubricity and/or anti-miciobial properties. The method comprises treating a polymer substrate in a diy atmosphere with a sufficient concentration ofSO3for a sufficient time to form a hydrophilic layer in said substrate, and substantially eliminating contact of said SO3with said substrate when a desired treatment of said polymer substrate has occurred to form a hydiophilic layer with at least one of said improved properties.
In another aspect of an embodiment of the present invention is a hydrophilic polymer substrate layer obtained by sulfonation with the formula: P-x wherein P is a polymer; and X is a polar functional group; wherein said layer imparts at least one of improved anti-fogging, anti-static, lubricity, wettability and/or anti-microbial properties. For purposes of this application, sulfonic groups are included in the definition of polar fimctional groups as used herein.
The layer fbrmed in a polymer according to at least one embodiment of the present invention can be imparted to a wide variety of polymer substrates without affecting transparency of the substrate. Accordingly, the process and articles formed according to the present invention find applicability in any areas such as sunglasses, ski and other protection goggles, such as eye or safety goggles, tail light lenses, head lamp lenses, helmet visors, lenses, contact lenses, transparent polymer covers, lids and fihns.
In addition, the invention finds application in medical arts, because substrates treated according to further embodiments of the present invention can be formed into articles such as catheters, intravenous bags, tubing, contact lenses, and valves to be implanted in the body; the articles formed with a hydrophilic layer obtained by sulfonation according to the present invention exhibit at least one of improved lubricity, wettability and anti-microbial properties.
Embodiment s of the present invention may be utilized to fbrni polymer pellets and powders that can be used to create other polymer substrates that have the hydrophilic layer obtained by sulfonation infused throughout. In addition, a polymer powder such as an acrylic powder, with a hydrophilic layer obtained by sulfonation can be used in paints or concrete retarding compositions. The improved wettability exhibited by such treated polymer powders can substantially reduce the amount of surfactants in such paints or concrete retanier solutions.
These and other aspects of the invention will become apparent upon a reading
of the following specification and examples.
One aspect, the present invention is a method for the preparation of a polymer substrate with at least one of improved anti-fogging, anti-static wettability, lubricity and anti-microbial properties. The invention includes treating a polymer substrate with a sufficient concentration of SO3 for a sufficient time to form a hydrophilic layer in said substrate and substantially eliminating contact of said SO3 with said substrate when a desired treatment of said polymer substmte has occurred to form a hydrophilic layer with at least one of said improved properties.
The sulfonation of the polymer substrate may be conducted in a batch or continuous process. In this regard, reference is made to pending US Patent Application No, 11/672,332 entitled "Method of Sulfonating an Article andRelated Apparatus" filed February 7,2007, assigned to the assignee of this application and incorporated herein by reference in its entirety. Specifically, in a batch process, a sulfonating chamber is provided wherein a polymer substrate is placed. Noble gasses such as argon or nitrogen, or dry air are used to purge the chamber and the polymer substrate in order to reduce moisture in the chamber. A sulfonating source, which may be gaseous or liquid, is introduced to the chamber and the substrate therein. The sulibnating source is preferably S03,and may be produced by the oxidation of SO2in the presence of at least one catalyst, such as, but not limited to V5O2and/or ultraviolet (UV) radiation. Sulfonation reagents also include: fuming sulfuric acid, stabilized SO3, such as amine stabilized, pyridine stabilized, trimethylsilyl sulfonyl chloride, sodium bisulfute pymlysis, commercially available SO3 and mixtures thereof. If in gaseous form, the SO3is introduced to said substrate in an amount of from about 0.5% by volume to about 20% by volume fora time period of about 5 seconds to about 30 minutes to form said hydrophilic layer. If in a liquid form, the SO3 is introduced to the polymer substrate for a time period of from about Isecond to about 10 minutes to form said hydrophilic layer. The reaction may proceed at ambient temperature and pressure. If desired, sufficient heat or UV radiation can be introduced to aid the sulfonation process to form a hydrophilic layer in said substrate. In this regard, it is contemplated that the temperature could range up to the glass transition temperature of the polymer substrate.
In order to improve the treatment of the polymersubstrate, the polymer substrate maybe exposed to organic solvents prior to sulfonation to enable more facile contact and reaction between the substrate and the SO3 to permit the hydrophilic layer to be imparted further into said polymer substrate. Examples of solvents can include, but are not limited to, acetone, hexanes and dichioromethane, polystyrene copolymers, derivatives of polystyrene copolymers, vinyl polymers, vinyl copolymers, derivatives of vinyl copolymers, and mixtures thereof.
The method may further include neutralizing the treated by sulfonation polymer substrate with a base to neutralize any residual sulfomc acid groups or other protic species. A suitable base may be selected from the group consisting of alanine, ammonia, dimethylamine, ethylarnine, glycine, hydrazine, methylamine, triethylamine, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, salts of weak organic and inorganic acids, metal bicarbonates, metal acid phosphates and diacid phosphates, metal citrates, metal acetates, metal ascorbates, derivates thereof, and mixtures thereof.
Although the advantages of the methods and articles of the present invention are not related to any particular theory, it is hypothesized that during sulfonation, hydrogen atoms and derivatives thereof which are bonded to carbon atoms in the hydrocarbons are replaced by sulfonic acid groups, where they become bonded and form a barrier layer. It may be that the hydrophilic polymer substrate layer obtained by sulfonation can be expressed by the formula: P-x wherein P is a polymer; and X is a polar functional group; wherein the layer imparts at least one of improved anti-fogging, anti-static, lubricity, wettability and/or anti-microbial properties. For purposes of this application, sulfonic groups are included in the definition of polar functional groups as used herein.
The bonds of the new layer material are nre polar, and therefore, are less likely to allow penneation of hydrocarbons. In one variation, this advantage is realized byusing polymeric materials which are sulfonatable by the methods of the present invention.
Suitable polymers for sulfonation may be selected from the group consisting of polycarbonates, derivatives of polycarbonates, alkylacrylates, alkylmethaciylates, derivatives of alkyl methaciylates, polyamides, polyimides, polyamido ethers, amido copolymers, polyimidoethers, imido copolymers, derivatives of imido copolymers, cellulosics, derivatives of cellulosics, polysulfones, derivatives of polysulfones, polyesters, copolymers of polyesters, allyl diglycol caibamates, polystyrenes, It is contemplated that the above described method can be used to impart a hydrophilic layer obtained by sulfonation to articles such as catheters, intravenous bags, tubing, contact lenses, and valves to impart improvement in at least one of lubricity and anti-microbial pmperties to said treated articles.
This method can also be used to impart a hydrephilic layer obtained by sulfonation to articles such as CDs, DVDs, High Definition DVDs, safety goggles, eyeglasses, sunglasses, ski glasses, and other optical media, packaging, contact lenses, automotive head lamp lenses, instrument panels, convertible top rear windows, tail lamp lenses and golf cart windshields to impart improvement in at least one of anti-static and anti-fogging properties to said articles.
Moreover, the method can be used to impart a hydrophilic layer obtained by sulfonation to polymer pellets and powders to impart at least improved wettability. When the powders are acrylic powders used in paints, the use of treated powders substantially reduces the use of surfactants in said paint. In addition the use of treated acrylic powders as concrete retarders substantially reduces the amount of surfactants used in concrete applications, such as oil well applications. When the polymer pellets are treated by sulfonation and subsequently fonned into articles, the hydrophilic layer is disbursed throughout the formed polymer substrate.
Objects and advantages of this invention are further illustrated by the following examples. The particular materials and amounts thereof, as well as other conditions and details, recited in these examples should not be used to limit this invention.
EXAMPLES
Polycarbonate substrates were treated utilizing SO3 created from a 20% by volume SO2 feedstock for 30 seconds in dry air up to about 10 minutes at 2% by volume SO2feedstock in dry air. The sulfonation chamber was purged with dry air before, between and after the sulfonation steps. The samples were neutralized by rinsing in water, in situ neutralization or with neutralization agents consisting of diluted solutions of weak basic reagents (salts of weak inorganic and organic acids, such as sodium bicarbonate, sodium citrate, sodium acetate) stronger bases such as group I metal hydroxides, ammonia, ammonia water. The samples were tested to determine the anti-ibg, wettabiity, anti-static and visual properties of the polymer substrate with ahydrophilic layerobtained by sulfonation. In order to determine anti-fogging properties, the hydrophilic layer obtained by sulfonation was subjected to fogging by a "hot fog or breath test" and the contact angle of the individual drops of condensed water were measured. The wettability was measured by the formation of water sheets rather than beading when water was applied to the samples. Anti-static was determined by visual inspection to determine whether treated samples attracted dust. Visual properties were determined by visual inspection of the samples after different periods of time or different treatments. All percents are by volume. The results are set forth in the following table.
TABLE 1
Contact Angle Measurements on Pure Polycarbonate (PC) Samples (All pH values measured at surface of sample) Sample Sul1nation Neutrahzation TreatiTest visual Ant-1bg Contt Properties Angles ________ _________ _______ _____ _______ (Avg) Pure PC N/A N/A pH 7.0 Clear None/fog 73.5 in <1 mm 01 3 mm 5% N/A; 1 wk @ Clear Initially 45.6 SO2 water rinse 95 C in w/tiny good poor feedstock in only oven; pH pits after oven dry air 7.0 before oven; loss of Iranspa rency after oven Sample Sulfonation Neutralization Treat/Test visual Anti-fbg Contact ?tope*ties Angles _____ ________ _________ _______ _____ _______ (Avg.) 02 3 mm, 5% N/A; N/A Clear Good> 30.6 vol, SO2 water rinse w/tiny 60s hot feedstock in only pits fog test ___ dryair _____ ____ ___ ____ ___ 03 6 miii, 5% 0.IM sodium N/A Clear Excellent 5*40 SO2, acetate 10 wltuny > 60s hot feedstock in mm, Ambient pits fog test _____ thy air Temp _______ _____ _______ _____ 04 6 mm, 5% 0.1 M sodium N/A Clear Excellent 8.0 SO2 acetate 60 w/tiny > 60s hot feedstock in mm, Ambient pits fog test _____ thy air Temp _______ _____ _______ _____ 6 mm, 5% 0.1 M sodium N/A Clear Excellent 5.0 SO2 acetate 10 w/tiny > 60s hot feedstock in mm, Ambient pits fog test ______ diy air Temp ________ ______ ________ ______ 06 6 mm, 5% 0.IM sodium N/A Clear Excellent 7.0 SO2 acetate 60 w/tiny > 60s hot feedstock in miii, Ambient pits lbg test ______ dry air Temp ________ ______ _________ ______ 07 5.5 miii, 2% 0.1M sodium N/A Clear Good> 30.9 SO2 acetate 10 w/tiny 60s hot feedstock in miii, Ambient pits fog test _____ thy air Temp _______ _____ _______ _____ 08 5.5 miii, 2% 0.1M sodium N/A Clear Good> 3 1.8 SO2 acetate 10 w/tuny 60s hot feedstock in mm, Ambient pits lbg test _____ dry air Temp _______ _____ _______ _____ 09 5 mm, 2% 0. IM sodium N/A Clear, Good> 11.1 SO2 acetate 10 no pits, 60s hot feedstock in mm, Ambient haze or fog test _____ thy air Temp _______ spots _______ _____ 10 mm, 2% 0.1 M sodium N/A haze Good> 7.9 SO2 acetate 10 60s hot feedstock in miii, Ambient fog test _____ dry air Temp _______ _____ _______ _____ Sample Sulfonation Neutralization Treat/Test visual Anti-tbg Contact Pmpethes An ______ ________ _________ _______ _____ _______ (Avg) 11 30s, 20% 0. 1M sodium 1 wk @ Clear, Good> 24.7 SO2 acetate 10 95 C in no pits 60s hot feedstock in mm, Ambient closed haze or fog test dry air Temp cont. pH spots 7.0 _________ ______ 12 3x20s, 13% 0.1M sodiwn 1 wk @ Clear, Very 8.0 SO2 acetate 10 95 C in no pits Good> feedstock in mm, Ambient closed haze or 60s hot dry air Temp cont. pH spots lbg test 7.0 ______ 13 3xlOs, 13% 0.IM sodium I wk @ Clear, Good 29.5 SO2 acetate 10 95 C in no pits feedstock in mm, Ambient closed haze or dry air Temp cont. pH spots 7.0 ______ 14 3x20s, 13% 0.1M 1 wk@ Clear, Good 18.8 SO2 bicarbonate 95 C in no pits feedstock in sol. I mm, closed haze or dry air Ambient cont. pH spots ______ __________ Temp 7.0 15 3mm, 5% 0.1M 1 wk @ Clear, Good 16.5 SO2 bicarbonate 95 C in no pits feedstock in sol. 6 mm, closed haze or dry air Ambient cont. pH spots ______ __________ Temp 7.0 16 2mm, 5% 0.1M N/A Clear, Increased, 34.1 SO2 bicarbonate no pits but not feedstock in sol. 10 mm, haze or excellent dry air Ambient spots _____ ________ Temp _______ _____ _______ _____ 17 imili, 13% 0.1M N/A Clear, Good 3 1.0 SO2 bicarbonate no pits feedstock in sol. 10 mm haze or dry air Ambient spots ______ _________ Temp _______ ______ _______ _____ Sample Sulfonation Neutralization Treat/Test viaual Anti-fbg Contact Properties Angles * .. . ________ ______... .. (Avg.) 18 4 miii, 2% 0.1M N/A Clear, Increased, 34.6 SO2 bicarbonate no pits but not feedstock in sol. 10 mm, haze or excellent dry air Ambient spots ______ ________ Temp _______ _____ _______ _____ 19 5 miii, 2% 0.1M N/A Clear, excellent 2-4 SO2 bicarbonate wlsligh feedstock in sol. 10 mm t dry air Ambient hazing Temp in some _____ ________ _________ _______ spots _______ _____ 4 mm, 2% 0.1M Water Clear Increased, N/A SO2 bicarbonate soak for 1 no pits, but not feedstock in sol. 10 mm, week @ haze or excellent dry air Ambient Ambient spots Temp temp. before! after Uv 21 4 mm, 2% 0.1M UV Clear Increased, N/A SO2 bicarbonate exposure no pits. but not feedstock in sol. 10 miii, outdoors A little excellent dry air Ambient (no rain, haze in Temp sunny spots weather, before/ I range after between water ________ ___________ _____________ 40-75 F) test As can be seen by reference to Table 1, surface hydrophilicity increased dramatically for polyvarbonate samples upon sulfonation. Polycarbonate samples treated by sulfonation can have contact angles that approach 0 while untreated samples have contact angles over 70 .
The breath test, hot ibg test, and wettability test show the formation of water sheets instead of beading and constitute additional evidence for increased h1rophilicity and anti-fog properties of polycarbonates treated by sulfonation. Moreover, it was observed that dust and other electrostatically charged particles did not accumulate on polycarbonate surfaces treated by sulfonation as they do on untreated polycarbonate surtces. Durability of the hydrophilic layer obtained by sulfonation was also demonstrated. Exposure ofpolycarbonate samples treated bysulfonation to heat in closed or open containers for up to a week did not deteriorate the visual aspect or decrease the anti-fog properties of samples treated by sulfonation if rinsed with a neutralizing solution after sulfonation. Exposure to outdoor UV light for 6 days did not lead to a decrease in anti-fog properties as assessed by wettability, hot fog and breath test. Finally, soaking in water at ambient temperature for 6 da did not lead to a decrease in anti-fog properties, as assessed by wettability, hot fog and breath tests.
While embodiments of the invention have been described and illustrated, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description, not words of limitation. It is understood that various changes and modification may be made without departing from the scope of the invention as set forth in the appended claims.
Claims (35)
1. A method for the preparation of a polymer substrate with at least one of improved anti-fogging, anti-static wettability, lubricity and/or anti-microbial properties, the method comprising: treating a polymer substrate witha sufficient concentration of SO3for a sufficient time to form a hydrophilic layer in said substrate; substantially eliminating contact of said SO3 with said substrate when a desired treatment of said polymer substrate has occurred to form a hydrophilic layer with at least one of said improved properties.
2. The method of claim 1, further including neutralizing saidpolymer substrate with a base to neutralize any residual sulfonic acid groups and other protic species.
3. The method of claim 2, wherein said base is selected from the group consisting of alanine, ammonia, dimethylamine, ethylamine, glycine, hydrazine, methylamine, triethylainine, lithium hydroxide, sodium hydroxide, potassium hydroxide, mbidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, salts of weak organic and inorganic acids, metal bicarbonates, metal acid phosphates and diacid phosphates, metal citrates, metal acetates, metal ascorbates, derivates thereof, and mixtures thereof.
4. The method of any preceding claim, wherein said polymer substrate is substantially clear, said polymer selected fim the group consisting of polycarbonates, derivatives of polycarbonates, alkylacrylates, alkylinethacrylates, derivatives of alkyl methaciylates, polyamides, polyimides, polyarrndo ethers, amido copolymers, polyimidoethers, imido copolymers, derivatives of imido copolymers, cellulosics, derivatives of cellulosics, polysulfones, derivatives of polysulfones, polyesters, copolymers of polyesters, allyl diglycol carbamates, polystyienes, polystyrene copolymers, derivatives of polystyrene copolymers, vinyl polymers, vinyl copolymers, derivatives of vinyl copolymers, and mixtures thereof.
5. The method of any preceding claim, wherein said SO3is gaseous or liquid,
6. The method of any preceding claim, wherein the sulfonation occurs in a dry atmosphere with suflicient SO3 to form a hydrophilic layer in the substrate,
7. The method of any preceding claim, wherein said SO3is produced by oxidation of SO2in the presence of at least one catalyst and/or UV radiation.
8. The method of any of claims 1 to 6, wherein said SO3is produced from a sulfonation reagent comprising: fuming sulfuric acid, stabilized SO3, such as amine stabilized, pyridine stabilized, Irimethylsilyl sulfonyl chloride, sodium bisulMepyrolysis, commercially available SO3, and/or mixtures thereof.
9. The method of any preceding claim, wherein said SO3is introduced to said substrate in an amount of from about 0.5% by volume to about 20 % by volume.
10. The method of any preceding claim, wherein said substrate is exposed to gaseous SO3for a time period of about 5 seconds to about 30 minutes to form said hydrophilic layer.
11 The method of any preceding claim, wherein said substrate is exposed to liquid SO3for a time period of from about 1 second to about 10 minutes to form said hydrophilic layer.
12. The method of any preceding claim, further including using sufficient heat or UV radiation to aid said sulfonation process to form a hydrophilic layer in said substrate.
13. The method of any preceding claim, further including the step of exposing the polymer substrate to organic solvents prior to sulfonation to enable more facile contact and reaction between the substrate and the SO3 to permit the hydrophilic layer to be imparted further into said polymer substrate.
14. The method of any preceding claim, wherein said hydrophilic layer obtained by sulfonation is imparted to articles such as any one of catheters, intravenous bags, tubing, contact lenses, and valves to impart improvement in at least one of lubricity and antimicrobial properties to said treated articles.
15. The method of any preceding claim, wherein said hydrophilic sulfonated layer is imparted to articles such as any one of CDs, DVDs, High Definition DVDs, safety goggles, eyeglasses, sunglasses, ski glasses, and other optical media, packaging, contact lenses automotive head lamp lenses, instrument panels, convertible top rear windows, tail lamp lenses and golf cart windshields to impart improvnent in at least one of anti-static and anti-fogging properties to said articles.
16. The method of any preceding claim, wherein said hydrophilic layer obtained by sulfonation is imparted to polymer pellets and powders to impart at least improved wettability.
17. The method of claim 16, wherein said powders are acrylic powders used in paints; said treated powders substantially reducing use of surfactants in paint.
18. The method of claim 16, wherein said powder is acrylic powder used as a retarder in concrete to substantially reduce the use of surfactants in said concrete.
19. The method of any preceding claim, wherein said preparation may be batch or continuous.
20. A hydrophilic polymer substrate layer with the formula: P-x wherein P is a polymer; and X is any polar functional group wherein said layer imparts at least one of improved anti-fogging, anti-static, lubricity, wettabiity and/or anti-microbial properties.
21. The hydrophilic polymer substrate layer of claim 20, wherein X is a sulfonic group.
22. The hydrophilic polymer substrate layer of claim 2Oor 21, wherein sulfonation of said substrate layer occurs in the presence of heat or (iv radiation.
23. The hydrophilic polymer substrate layer obtained bysulfonation of anyof claims to 22, wherein said polymer substrate is selected from the group consisting of polycarbonates, derivatives of polycarbonates, alkylacrylates, alkylniethaciylates, derivatives of alkyl methactylates, polyarnides, polyimides, polyamidoethers, amido copolymers, potyimidoethers, imido copolymers, derivatives ofimido copolymers, cellulosics, derivatives ofcellulosics, polysulfones, derivative ofpolysulfones, polyesters, copolymers of polyesters, ally! diglycolcarbamates, polystyrenes, polystyrene copolymers, derivatives of polystyrene copolymers, vinyl polymers, vinyl copolymers, derivatives of vinyl copolymers, and mixtures thereof.
24. The hydrophilic polymer substrate layer obtained bysulfonation of anyof claims to 23, wherein said treated polymer substrate layer is further treated with a base to neutralize any residual sulfonic acid groups and/or other protic species.
25. The.hydrophil Ic polymer substrate layer obtained by sulfonation of claim 24, said base selected from the group consisting of alanine, ammonia, dimethyl amine, ethylamine, glycine, hydrazine, methylamine, triethylamine; lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, salts of weak organic and inorganic acids, metal bicarbonates, metal acid phosphates, and diacid phosphates, metal citrates, metal acetates, metal ascorbates, and mixtures thereof.
26. The hydrophilic polymer substmte layer obtained bysulfonation of anyof claims to 25, wherein said SO3 is produced by oxidation of SO2 in the presence of at least one catalyst and/or UV radiation.
27. The hydrophilic polymer substrate layer obtained bysulfonation of anyof claims to 25, wherein said SO3 is produced from a sulfonation reagent comprising: fuming sulfuric acid, stabilized SO3, such as amine stabilized, pyridine stabilized, trimethylsilyl sulfonyl chlOride, sodium bisulfate pyrolysis, commercially available SO3, and/or mixtures thereof.
28. The hydrophilic polymer subslmte layer obtained bysulfonation of anyof claims to 27, wherein said layer is imparted to articles such as catheters, intravenous bags, contact lenses and valves to impart improved at least one of lubricity, anti-fogging, and anti-microbial properties to said articles.
29. The hydrophilic substrate layer obtained by sulfonation of any of claims 20 to 28, wherein said layer is imparted to articles such as CDs, DVDs, High Definition DVDs, and optical media to impart at least improved anti-static properties to said articles.
30. The hydrophilic substrate layer obtained by sulfonation of any of claims 20 to 29, wherein said layer is imparted to an article such as safety goggles, eyeglasses, sunglasses, packaging, automotive headlamp lenses, instrumt panels, convertible top rear windows, tail lamp lenses and golf cart windshields to impart at least improved anti-fogging properties to said articles.
31. The hydrophilic substrate layer obtained by sulfonation of any of claims 20 to 30, wherein said layer is imparted to polymer pellets and powders to impart at least improved wettability to said pellets and powders.
32. The hydrophilic substrate layer obtained bysulfonation of claim 31, wherein said powders are acrylic powders used in paints to substantially reduce the use of surfactants in said paint.
33. The hydrophilic substrate layerobtained by sulfonation ofclaim 31, wherein said powders are acrylic powders used in concrete as retarders to reduce the use ofsurfactants in said concrete.
34. A method substantially as hereinbefore described.
35. A polymer layer substantially as hereinbefore described.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US88509107P | 2007-01-16 | 2007-01-16 | |
US11/672,332 US7578953B2 (en) | 2006-02-07 | 2007-02-07 | Method of sulfonating an article and related apparatus |
US11/748,252 US20080171835A1 (en) | 2007-01-16 | 2007-05-14 | Method of sulfonation of polymer substrate to impart a hydrophilic layer in said substrate with improvement in at least one of anti-fog, anti-static, wettability, lubricity anti-microbial properties, and articles made thereby |
Publications (3)
Publication Number | Publication Date |
---|---|
GB0800648D0 GB0800648D0 (en) | 2008-02-20 |
GB2445854A true GB2445854A (en) | 2008-07-23 |
GB2445854A8 GB2445854A8 (en) | 2009-04-01 |
Family
ID=39144926
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB0800648A Withdrawn GB2445854A (en) | 2007-01-16 | 2008-01-15 | Hydrophilic polymer substrates |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2445854A (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1218999A (en) * | 1967-11-29 | 1971-01-13 | Dow Chemical Co | Transparent astatic resinous articles and method for their production |
EP0045323A1 (en) * | 1980-08-02 | 1982-02-10 | The Dow Chemical Company | Improved process for sulfonating solid organic polymers |
JPS6377946A (en) * | 1986-09-19 | 1988-04-08 | Tokuo Saito | Method of imparting antistatic property to plastic material |
WO1997026284A1 (en) * | 1996-01-16 | 1997-07-24 | Memtec America Corporation | Method for gas phase sulfonation of polymer membranes |
JPH11315158A (en) * | 1998-05-06 | 1999-11-16 | Tokuo Saito | Antistatic finish of synthetic resin containing or not, containing aryl group |
JP2002105852A (en) * | 2000-09-25 | 2002-04-10 | Japan Wool Textile Co Ltd | Method for modifying synthetic fiber and synthetic resin with sulfur trioxde in vapor-phase |
-
2008
- 2008-01-15 GB GB0800648A patent/GB2445854A/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1218999A (en) * | 1967-11-29 | 1971-01-13 | Dow Chemical Co | Transparent astatic resinous articles and method for their production |
EP0045323A1 (en) * | 1980-08-02 | 1982-02-10 | The Dow Chemical Company | Improved process for sulfonating solid organic polymers |
JPS6377946A (en) * | 1986-09-19 | 1988-04-08 | Tokuo Saito | Method of imparting antistatic property to plastic material |
WO1997026284A1 (en) * | 1996-01-16 | 1997-07-24 | Memtec America Corporation | Method for gas phase sulfonation of polymer membranes |
JPH11315158A (en) * | 1998-05-06 | 1999-11-16 | Tokuo Saito | Antistatic finish of synthetic resin containing or not, containing aryl group |
JP2002105852A (en) * | 2000-09-25 | 2002-04-10 | Japan Wool Textile Co Ltd | Method for modifying synthetic fiber and synthetic resin with sulfur trioxde in vapor-phase |
Also Published As
Publication number | Publication date |
---|---|
GB2445854A8 (en) | 2009-04-01 |
GB0800648D0 (en) | 2008-02-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3992763B2 (en) | Water-repellent surface treatment with integrated undercoat | |
EP2522702B1 (en) | Anti-fog coating composition | |
US5804612A (en) | Transparent anti-fog coating | |
JP2011530401A (en) | Acicular silica coating to increase hydrophilicity / permeability | |
EP1154287A2 (en) | Oxygen permeable contact lens having a hydrophilic surface and method for producing the same | |
JP2019026825A (en) | Copolymer, coating composition, and article | |
JP5881828B2 (en) | Hydrophilic modified acrylic resin film | |
US20080171835A1 (en) | Method of sulfonation of polymer substrate to impart a hydrophilic layer in said substrate with improvement in at least one of anti-fog, anti-static, wettability, lubricity anti-microbial properties, and articles made thereby | |
US20090246513A1 (en) | Process for Producing Anti-Fog Coating | |
US20070098906A1 (en) | Inorganic coating composition and hydrophilic coating film | |
WO2008079495A2 (en) | Coatings and solutions for contact lenses | |
US9150766B2 (en) | Moisture absorbing anti-fog composition and process for the use thereof | |
JP4431199B2 (en) | Surface treatment agent composition, surface treatment method, substrate, and article | |
JP7209086B2 (en) | Anti-fog coating composition, anti-fog coating film and anti-fog article | |
CN109251272B (en) | Method for applying bionic self-assembled polymer microspheres to anti-fog coating | |
GB2445854A (en) | Hydrophilic polymer substrates | |
KR950014730B1 (en) | Composition of utraviolet luring antifogging agent and process for forming antifogging coating film | |
JP4524936B2 (en) | Method for imparting antifogging performance and optical article | |
JPH0726062B2 (en) | Surface treatment agent for inorganic coated film | |
KR20020007410A (en) | Method and agent for producing hydrophobic layers on fluoride layers | |
JPH08277379A (en) | Silica-based coating material | |
Meng et al. | Superhydrophilic multifunctional antifogging coatings based on triethoxysilyl-terminated poly (N-vinylpyrrolidone) | |
CN112437789B (en) | Sulfonate-functional coating compositions, methods of making, and articles made therefrom | |
JPH0976428A (en) | Agricultural anti-fogging film | |
JPH0335031A (en) | Method for imparting anti-fogging property |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |