MXPA99008718A - Transparent fluorinated polyurethane coating compositions and methods of use thereof - Google Patents
Transparent fluorinated polyurethane coating compositions and methods of use thereofInfo
- Publication number
- MXPA99008718A MXPA99008718A MXPA/A/1999/008718A MX9908718A MXPA99008718A MX PA99008718 A MXPA99008718 A MX PA99008718A MX 9908718 A MX9908718 A MX 9908718A MX PA99008718 A MXPA99008718 A MX PA99008718A
- Authority
- MX
- Mexico
- Prior art keywords
- fluorinated
- composition according
- composition
- polyol
- transparent
- Prior art date
Links
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims description 201
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000008199 coating composition Substances 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 15
- 230000003287 optical Effects 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- 230000002411 adverse Effects 0.000 claims abstract description 3
- 229920005862 polyol Polymers 0.000 claims description 104
- 150000003077 polyols Chemical class 0.000 claims description 100
- 150000001875 compounds Chemical class 0.000 claims description 54
- 125000001931 aliphatic group Chemical group 0.000 claims description 25
- 238000007711 solidification Methods 0.000 claims description 25
- -1 alkynyl radical Chemical class 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 24
- 229920001228 Polyisocyanate Polymers 0.000 claims description 20
- 239000005056 polyisocyanate Substances 0.000 claims description 20
- 229920001774 Perfluoroether Polymers 0.000 claims description 16
- 150000001298 alcohols Chemical class 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-Propanediol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N 1,6-Hexanediol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-Dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentanediol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- VLNDSAWYJSNKOU-UHFFFAOYSA-N 1-isocyanato-4-[(4-isocyanato-3-methylcyclohexyl)methyl]-2-methylcyclohexane Chemical compound C1CC(N=C=O)C(C)CC1CC1CC(C)C(N=C=O)CC1 VLNDSAWYJSNKOU-UHFFFAOYSA-N 0.000 claims description 2
- LYDHLGJJJAWBDY-UHFFFAOYSA-N 1-isocyanato-4-[2-(4-isocyanatocyclohexyl)propan-2-yl]cyclohexane Chemical compound C1CC(N=C=O)CCC1C(C)(C)C1CCC(N=C=O)CC1 LYDHLGJJJAWBDY-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N Hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N Isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 230000001747 exhibiting Effects 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 description 43
- 239000004814 polyurethane Substances 0.000 description 43
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 39
- 239000000126 substance Substances 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229920001610 polycaprolactone Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000002009 diols Chemical class 0.000 description 9
- 239000004632 polycaprolactone Substances 0.000 description 9
- 150000004072 triols Chemical class 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000002093 peripheral Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007655 standard test method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 230000002209 hydrophobic Effects 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000011253 protective coating Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000004059 degradation Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000003628 erosive Effects 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- UJMWVICAENGCRF-UHFFFAOYSA-N Oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N Palmitic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- CWZSSTXVRMPSLX-UHFFFAOYSA-M dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O CWZSSTXVRMPSLX-UHFFFAOYSA-M 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged Effects 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- YPJRYQGOKHKNKZ-UHFFFAOYSA-N 1-ethyl-1-methylcyclohexane Chemical compound CCC1(C)CCCCC1 YPJRYQGOKHKNKZ-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Azelaic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000002730 additional Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 230000000111 anti-oxidant Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001143 conditioned Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 231100000078 corrosive Toxicity 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010192 crystallographic characterization Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- LMCBEWMQFKWHGU-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O LMCBEWMQFKWHGU-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reduced Effects 0.000 description 1
- 230000003252 repetitive Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000003381 solubilizing Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- USPTVMVRNZEXCP-UHFFFAOYSA-N sulfamoyl fluoride Chemical compound NS(F)(=O)=O USPTVMVRNZEXCP-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
In accordance with the present invention, there are provided coating compositions for preparing cross-linked fluorinated polyurethane coatings and liners that exhibit high optical clarity and transparency, as well as resilience against adverse environmental effects. The present invention also provides methods for coating solid substrates with transparent, environmentally-resistant cross-linked, fluorinated polyurethane coatings, as well as the resulting coated articles.
Description
COMPOSITIONS OF TRANSPARENT POLYURETHANE POLYURETHANE COATINGS AND METHODS FOR USING THEMSELVES
FIELD OF THE INVENTION The present invention relates to coating compositions which, when solidified, form trans-entained fluorinated polyurethane coatings that are weather and chemical resistant, hydrophobic, as well as transparent, as well as methods for coating solid substrates with these compositions. of coating and articles that have hydrophobic coating resistant to weather and transparent chemicals.
BACKGROUND OF THE INVENTION Aircraft and military land vehicles are often required to operate under hostile environmental conditions. After prolonged exposure to these conditions, the windows of these vehicles, whether made of glass or plastic, tend to scratch and sting due to abrasion and the erosive effects of rain, hail, sand, dust and the like. Plastic surfaces are also susceptible to damage from chemical exposure. As a result, the visibility through these exposed surfaces becomes substantially impaired. To mitigate against the adverse effects of various operating conditions, efforts have been made to create effective protective coatings for various types of exposed surfaces. Unfortunately, these efforts have been made with limited success.
Strong coatings and thermoset polyurethane films, sometimes referred to as "liners", exemplify a type of transparent coating system that has been used to protect glass and plastic surfaces against erosion and abrasion of particles. Although they are effective in reducing the damage caused by abrasion and erosion, they are often not durable enough to withstand the effects of exposure to the environment (ie, long-term exposure to outdoor environmental conditions) or exposure to chemical The durable exterior exposure not only causes a yellowing of the polyurethane material, but also promotes its degradation with respect to both transparency and mechanical durability. Conventional polyurethane coatings are also damaged by some organic chemicals and strong acids, resulting in degraded vision quality.
Another disadvantage of using polyurethane as a protective coating material is that polyurethane surfaces are more difficult to clean, compared to transparent plastic or glass surfaces. This problem worsens with prolonged exposure to the weather. Specifically, as the polyurethane surfaces are exposed to the environment, they become harsh. The grime thus adheres to these rough surfaces which makes cleaning difficult, causing further degradation of the window's viewing quality. These limitations have thus limited the use of polyurethane coatings in cargo aircraft windows.
According to the above, there is a need for protective coatings which are both environmentally friendly and transparent.
BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, we have developed coating compositions for improving the durability in the environment of a substrate and methods for coating said substrates by applying a coating composition which, after solidifying, forms a coating strong fluorinated polyurethane transenlazado that is highly resistant to weather and chemicals, hydrophobic, as well as transparent. In accordance with another aspect of the present invention, we have developed articles that have hydrophobic, transparent and yet highly weather resistant coatings and chemicals on them. The coating compositions of the present invention are useful in applications where optical clarity and resistance to environmental effects are highly desirable, such as, for example, as protective coatings for aircraft transparencies, or for windows of automobiles and other land vehicles.
DETAILED DESCRIPTION OF THE INVENTION According to the present invention, there is provided a coating composition comprising: (A) an aliphatic polyisocyanate; (B) a non-fluorinated polyol; and (C) an aliphatic fluorinated hydroxy functional compound selected from the group consisting of a fluorinated alcohol, a fluorinated polyol and mixtures thereof, wherein after said application to a substrate and its subsequent solidification, said coating composition forms a coating of transparent and translucent fluorinated polyurethane having a glass transition temperature of at least about -30 ° C.
The aliphatic polyisocyanates contemplated for use in the practice of the present invention include, for example, linear, branched and cyclic aliphatic compounds containing two or more isocyanate groups, as well as combinations of any two or more of them. Exemplary aliphatic polyisocyanates include, for example, 4,4'-methylene-bis- (cyclohexyl isocyanate), 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 1-4-butane diisocyanate, 1,6-hexane diisocyanate, 1,10 -decano diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate, bis- (3-methyl-4-isocyanato-cyclohexyl) methane, 2,2-bis- (4-isocyanatocyclohexyl) propane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-dicyclohexyl diisocyanate, 2,4-dicyclohexyl diisocyanate and the like, as well as combinations of any two or more thereof. Cycloaliphatic diisocyanates and 4,4'-methylene-bis- (cyclohexyl isocyanate) are especially preferred.
The amount of polyisocyanate in the coating composition of the invention can vary widely in relation to the amounts of the other components of the composition. Typically, the amount of polyisocyanate is such that the ratio of the groups - NCO - with the total OH groups in the coating composition of the invention is between about 1.5: 1 and about 1: 1. Preferably the proportion of the groups - NCO - with the total OH groups in the compositions of the present invention is between about 1.1: 1 and about 1: 1.
The amount of aliphatic polyisocyanate employed in the coating compositions of the present invention is typically within the range of about 10 and about 60 weight percent, based on the total weight of the coating composition. Preferably, the amount of aliphatic polyisocyanate is within the range of about 25 and about 50 percent by weight, based on the total weight of the coating composition. More preferably, the aliphatic polyisocyanate is employed in the coating compositions of the invention in amounts within the range of about 35 and about 40 percent by weight, based on the total weight of the coating composition.
As used herein, the term "non-fluorinated polyol" refers to a monomeric or polymeric non-fluorinated organic compound having hydroxyl functionality of two or more (eg, diols, triols, and compounds having a hydroxyl functionality of four. or more), and mixtures thereof. As used herein, the term "monomeric" refers to an organic compound of relatively low molecular weight. The term "polymeric", as used herein, refers to an organic compound containing repetitive monomer units and having a molecular weight of 300 or greater.
Suitable non-fluorinated monomeric polyols include compounds, such as, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,12-decanediol, 2, 2-dimethyl-propane-1,3-diol, 1,4-cyclohexane-dimethylol, trimethylpropane and the like, as well as combinations of any two or more thereof.
Exemplary non-fluorinated polymer polyols include polyether polyols, polyester polyols, polycarbonate polyols and the like, as well as combinations of any two or more thereof. Non-fluorinated polyether polyols which are suitable for use in the practice of the present invention include, for example, polyol poly (ethylene oxide), polyol poly (1,2-propylene oxide), polyol poly (tetramethylene oxide) and the like, as well. as also combinations of any two or more thereof.
Polyester polyols contemplated for use in the practice of the present invention include, for example, polycaprolactone polyols, esterification products of low molecular weight diacids (such as, for example, adipic acid, succinic acid, palmitic acid, azelaic acid, acid sebacic and the like, as well as combinations of any two or more thereof) and diols (as is, for example, ethylene glycol, propane-1,3-diol, butane-1,4-diol, hexane-1,6 diol, 1,6-cyclohexane diol and the like, as well as combinations of any two or more thereof) and the like and mixtures thereof.
Exemplary polycaprolactone polyols contemplated for use in the practice of the present invention include polyols having the general formulas (I) and (II): (I) H - (O - (CH2) n - (OC)) mO - Rx - O ((CO) (XH2) n -O) pH; and (TI) R2 - [O ((CO) (CH2) n -O) m-H] 3, wherein Ri is chosen from an optionally substituted branched or straight chain, alkyl, alkenyl or alkynyl, divalent radical, having from about 1 to about 20 carbon atoms in the main element, R2 is chosen from an optionally substituted branched or straight chain, alkyl, alkenyl or alkynyl, trivalent radical, having from about 1 to about 20 carbon atoms in the main element, yn, m and p are integers chosen so that the molecular weight of the compounds encompassed by (I) and (II) is between about 300 and 10,000 g / mole. Preferably n, m and p are chosen so that the molecular weight of the compounds encompassed by (I) and (II) is between about 300 and about 5,000 g / mole and more preferably between about 500 and about 2,000 g / mole. mass.
As used herein, the terms "molecular weight" and "average molecular weight" are used interchangeably to refer to the molecular weight of a component.
Suitable polycarbonate polyols contemplated for use in the practice of the present invention include polyols having the general formula (III): (III) [HO - (R3-O- (CO) -O-) n] m -R4 wherein R3 is independently chosen from an optionally substituted branched or straight chain, alkyl, alkenyl or alkynyl divalent radical, having from about 1 to about 20 carbon atoms in the main element, R4 is selected from a branched chain or optionally substituted alkyl, alkenyl or alkynyl of divalent or trivalent radical, having from about 1 to about 20 carbon atoms in the main element, m is an integer chosen from 2 or 3, and n is chosen so that the Molecular weight of the compounds encompassed by (HI) is between about 200 and about 10,000 g / mole, preferably between about 300 and about 5,000 g / mole and more preferably between about 300 and about 2,000 g / m ole
The polyols encompassed by the formulas (I), (II) and (TU) which are preferred for use in the practice of the present invention include, for example, the products sold under the names Tone 200® and Tone 210® (formula ( I)) (Union Carbide Corp., Specialty Polymers and Composites Div., Danbury, Connecticut); Tone 301® and Tone 305® (Formula (II)) (Union Carbide Corp., Specialty Polymers and Composites Div., Danbury, Connecticut); and Ravercarb® 207 (Formula (III)) (Enichem Synthesis S.p.A., Milan, Italy).
The non-fluorinated polymeric polyols employed in the practice of the present invention typically have an average molecular weight in the range of about 300 to about 10,000 g / mole. Preferably, the non-fluorinated polymeric polyols used in the compositions of the present invention have molecular weights in the range of about 300 and about 5,000 g / mole. More preferably, the non-fluorinated polymeric polyols employed in the compositions of the invention have molecular weights in the range of from about 500 to about 2,000 g / mole.
The amount of non-fluorinated polyol (s) will vary depending on the type of non-fluorinated polyols employed. In general, based on weight, the amount of non-fluorinated polyol used in the compositions of the invention is higher for higher molecular weight polyols (eg, polymeric polyols), as compared to low molecular weight polyols (eg, polyols). example, monomeric polyols). Typically, the total amount of the non-fluorinated polyol employed is between about 1 and about 90 percent by weight, based on the total weight of the coating composition. Preferably the amount of non-fluorinated polyol used in the compositions of the present invention is between about 2 and about 80 percent by weight, based on the total weight of the coating composition, and is more preferred between about 2. and about 7o percent by weight, based on the total weight of the coating composition.
As used herein, the term "fluorinated aliphatic hydroxy functional compound" refers to an aliphatic compound having one or more hydroxy functional groups, with fluorine atoms coupled to one or more carbon atoms. Aliphatic fluorinated hydroxy functional compounds include, for example, aliphatic fluorinated alcohols, aliphatic fluorinated polyols (ie, compounds having hydroxyl functionality of two or more) and mixtures thereof. As contemplated in the practice of the present invention, the fluorinated aliphatic hydroxy functional compounds may be either monomeric (low molecular weight or polymeric.
The degree of fluorination of the aliphatic fluorinated functional hydroxy compounds can be varied such that both partially fluorinated or perfluorinated aliphatic hydroxy functional compounds are suitable for use in the practice of the present invention. As used herein, the term "perfluorinated" refers to a fluorocarbon compound in which the hydrogen atoms directly attached to the carbon atom are completely replaced with fluorine atoms.
The aliphatic fluorinated hydroxy functional compounds that are employed in the practice of the present invention can be either straight or branched chain, and typically have a molecular weight in the range of about 100 to about 20,000 g / mole. Preferably, the aliphatic fluorinated hydroxy functional compounds of the present invention have molecular weights in the range of about 150 to about 10,000 g / mole, and more preferably in the range of about 300 and about 5,000 g / mole.
Exemplary aliphatic fluorinated alcohols include fluoroalkane alcohols, fluoroether alcohols, fluorosulfonamide alcohols, and the like, as well as combinations of any two or more thereof. Preferred fluoroalkane alcohols include those having the general formula: (IV) CF3 - (CF2) n - CH2CH2 - OH wherein n is a number between about 1 and about 10, and more preferably between about 3 and about 8. Fluoroalkane alcohols having the formula (TV) are available from DuPont Specialty Chemicals (Wilmingotn,
Delaware) under the product name Zonil® BA (n = & 8 most; MWt = 404 g / mole) and Zonyl® BAL (n = 6 majority; MWt = 443 g / mole).
Preferred fluoroether alcohols contemplated for use in the practice of the present invention include those having the formulas: CF3 I (V) CF3 -O- (CF2-CF-O) "-CH2-CH2-OH; (VI) CF3-O - [(CF2) 4-O-] "- CH2CH2-OH; CF3 I (VII) CF3 - O - (CF2 CF - O -) ". CF2-O-) m CF2 CH2-OH; and mixtures thereof, wherein m and n are chosen independently of the numbers within the range of about 1 to about 4. An exceptional fluoroether alcohol has the formula (VII) employed in the practice of the present invention is available from Ausimont SpA (Milan, Italy) under the name Fomblin® MF-402 (m = 3, n = 1.5, MWt = 712 g / mole). However, Fomblin® MF-402 is not suitable for use in the compositions of the invention in which non-fluorinated polycaprolactone polyols of the formulas (I) and (II) are also used.
The fluoro-sulfonamide alcohols contemplated for use in the practice of the present invention include compounds having the general formula: (Vm) R5-SO2-N-R5-OH I
RT wherein R5 is chosen from branched or optionally substituted fluorinated or partially fluorinated chain, alkyl, alkenyl or alkynyl radical having from about 1 to about 20 carbon atoms in the main element, e is chosen from a branched chain or optionally substituted fiuorinated radical, divalent alkyl, alkenyl or alkynyl radical having from about 1 to about 20 carbon atoms in the main element, and R7 is selected from a hydrogen atom, an optionally substituted, optionally fluorinated or branched chain optionally , alkyl, alkenyl or alkynyl radical having from about 1 to about 20 carbon atoms in the main element.
An aliphatic fluorosulfonamide alcohol having the formula (VIII) which is preferred for use in the practice of the present invention has the formula: (IX) CF 3 - (CF 2) 7 -SO 2 - N - (CH 2) 2 -OH I (CH2CH3) available, for example, from 3M Corporation (St. Paul, Minnesota) under the name Fluorad® FC-10).
As used herein, the term "fluorinated aliphatic polyol" refers to a monomeric or fluorinated polymeric organic compound having hydroxyl functionality of two or more (eg, diols, triols, and compounds having a hydroxyl functionality of four. or more). Suitable aliphatic fluorinated polyols include, for example, fluoroalkane polyols, fluoroether polyols, fluoro-sulfonamide polyols, fluorinated vinyl alcohol polymers and copolymers thereof, and the like, as well as combinations of any two or more thereof.
Fluoroalkane polyols which are suitable for use in the practice of the present invention include, for example, polyols having the general formulas: (X) HO - (CH 2) n - (CF 2) m - (CH 2) P - OH; (XI) HO - (CH2) "- CH - (CH2) m - (CF2) P - CF3; I OH
CF3 CF3 I I (XH) HO - CH2 - CH2 - (CF - CF2) n - (CF2) ra - (CF - CF2) P - CH2CH2 - OH; and mixtures thereof, wherein m, n and p are chosen so that the molecular weight of the compounds encompassed by (X) - (XII) is between about 100 and about 3,000 g / mole. Preferably, n, m and p are chosen so that the molecular weight of the compounds encompassed by (X) - (XII) is between about 100 and about 2,000 g / mole, and more preferably, between about 100 and about 1,000 g / mole.
Fluoroalkane polyols that are preferred for use in the practice of the present invention include compounds having the formulas: HO-CH 2 - (CF 2) - CFJ-OH, HO
- CH2 - (CF2) 3 - CH2 - OH, and HO - CH2 - (CF2) 2 - CH2 - OH (ie, the formula (X)); HO
- CH2CH (OH) - CH2 - (CF2) 5CF3) (ie, 3-perfluorohexyl-propane-1-1,2-diol (formula (XI)); and the compound having the formula HO-CH2CH2 - (CF2 ) s-CF (CF3) -CH2-CH2-OH (ie, formula (XII)) (although Formula XII in particular is not suitable for use in conjunction with the non-fluorinated polyols of the formulas (I ) and (II)) - Fluoroether polyols contemplated for use in the practice of the present invention include fluorinated compounds having the following general formulas: (Xm) HO - (CH2) rCF2 - O - [(CF2) nO] m - [(CF2) pO] q - CF2 (CH2) r - OH where r is 1 or 2, n, m, p and q are chosen such that the molecular weight of the compounds encompassed by (XIII) is between about 500 and about 5,000 g / mole, and wherein m / q is at least about 0.9.Most preferably, m / q is at least equal to
1. Preferably, n, m, p and q are chosen so that the molecular weight of the compounds encompassed by (Xffl) is between about 500 and about 3,000 g / mole, and more preferably between about 500 and about 2,000 g. /mass; Y
CF3 I (XIV) HO-CH2-CF2 -O- (CF2-CF-O) "-O-CF2CH2-OH, wherein n is chosen such that the molecular weight of the compounds encompassed by (XrV) is between of 500 and about 5,000 g / mole, preferably between about 500 and about 3,000 g / mole, and more preferably between about 500 and about 2,000 g / mole.
A fluorinated polyol of the present invention encompassed by (XIII), which is preferred for use in the practice of the present invention, is the polyol having the formula HO -CH2CF2-O - [(CF2) 2O] 6 - [(CF2 ) O)] 6-CF2CH2-OH (available, for example, from Ausimont, SpA, Milan, Italy, under the name Fluorobase® Z-1030).
Typically, the aliphatic fluorinated hydroxy functional compounds are employed in compositions of the present invention in an amount within the range of about
1 to about 85 percent by weight, based on the total weight of the composition. Preferably, the amount of the aliphatic fluorinated hydroxy functional compounds employed in the invention is within the range of from about 3 to about 70 percent by weight, based on the total weight of the compositions. More preferably, the aliphatic fluorinated hydroxy functional compounds are employed in the compositions of the invention in a total amount ranging from about 3 to about 60 weight percent, based on the total weight of the composition.
Optionally, the coating compositions herein may contain additives, such as, for example, inking agents, absorbers or UV blockers, antioxidants, antiaesthetic agents and the like, as well as combinations of any two or more thereof. Specific chemical compounds having the functions described above can be easily identified by those of ordinary skill in the art.
The coating compositions of the present invention typically contain a solidifying catalyst. As used herein, the term "solidifying catalyst" refers to an agent that promotes polymerization. Solidifying catalyst agents include tin derivatives (for example, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, and the like), iron derivatives (e.g., ferroacetylacetonate, and the like), titanium alcoholates (e.g. titanium tetraisopropylate and the like), tertiary amines (e.g., triethylamine, and the like) and the like, as well as combinations of any two or more thereof.
The actual amount of the solidifying catalyst can vary widely and is typically up to about 0.01 percent by weight, based on the total weight of the composition. Preferably the amount of the solidifying catalyst employed in the compositions of the invention is within the range of about 0.001 to about 0.005 percent, of the total weight of the composition.
The components of the composition can be mixed together without any pre-reaction step in a "one step" process, or alternatively, one or more polymers can be optionally prepared from one or more of the components of the invention for subsequent mixing with the remaining composition components. As used herein, the term "prepolymer" refers to reactive chemical species that are partially polymerized (ie, a species that retains additional polymerizable functionality). The prepolymers are prepared by allowing one or more of the components of the composition of the invention to partially polymerize.
A "two stage" mixing process can be employed when a prepolymer is used in compositions of the present invention. Thus, for example, a prepolymer of aliphatic polysiocyanates and aliphatic fluorinated hydroxy functional compounds can be prepared first, then combined with one or more fluorinated polyols, and optionally, polyisocyanates and / or additional aliphatic fluorinated functional hydroxy functional compounds. As an alternative, a prepolymer of aliphatic polyisocyanates and non-fluorinated polyols can be prepared first, then they can be combined with one or more fluorinated aliphatic hydroxy functional compounds, and optionally, aliphatic polyisocyanate and / or additional aliphatic fluorinated hydroxy functional polyol. The prepolymer is typically prepared so that the ratio of total-NCO-groups to total -OH groups is about 1.5: 1.0 or greater.
The "two step" process is preferred, for example, when one or more of the components of the composition of the invention is insoluble with the rest of the composition, but when a prepolymer of the insoluble components is currently soluble with the other components of the composition. The "two stage" process is also preferred when increased viscosity is desired due to processing considerations.
Optionally, it is sometimes desirable to incorporate compatible solvents in the compositions of the invention, for example, to modify the viscosity of the coating composition to facilitate the coating process, to modify the kinetics of the solidification process, to modify the thickness of the coating solidified and similar. As used herein, the term "compatible solvent" refers to a solvent that does not induce substantial phase separation of the components of the composition during the solidification process, does not react with the polyisocyanate and does not induce cracking (or any other type of damage) in the substrate material.
Compatible solvents are thus capable of solubilizing components of the composition of the invention, and in addition, are capable of thickening partially or completely solidified coatings of the present invention. Those of ordinary skill in the art will appreciate that the particular solvent employed must also be compatible with the particular substrate used. For example, when acrylic and polycarbonate substrates are used, suitable solvents include those that will not solubilize acrylic or polycarbonate, such as, for example, propylene glycol, monomethyl ether acetate, 2-ethoxyethyl acetate, and the like. The preferred solvents for use when using glass substrates are ethyl methyl ketone, cyclohexane and ethyl acetate.
Solvents are not required to produce the transparent weather resistant coatings of the present invention. As demonstrated in the examples given below, transparent weather resistant coatings can be easily prepared from compositions of the invention that are either solvent-free or substantially solvent-free.
In accordance with another aspect of the present invention, there is provided a method for coating a solid substrate comprising: (i) preparing a coated substrate by contacting a surface of a solid substrate with a coating composition that forms a polyurethane coating transparent trans-enameled fluorinated, said coating composition comprises: (A) an aliphatic polyisocyanate; (B) a non-fluorinated polyol; and (C) an aliphatic fluorinated hydroxy functional compound as described herein; then (ii) subjecting said coated substrate to solidification conditions such that said composition forms a transparent trans-entangled fluorinated polyurethane coating having a glass transition temperature of at least -30 ° C.
Solid substrates suitable for use in the practice of the present invention include those made of glass and polymeric materials. Useful polymeric substrates include polycarbonates, acrylics, polyesters, cellulosics, styrene-acrylonitrile copolymers and their derivatives, polyurethane plastics and the like.
The term "contacting", as used herein, refers to the application of the coating composition to the substrate. Appropriate methods for contacting a solid substrate with the coating compositions of the present invention include dip coating, roll coating, plating, flow coating, curtain coating, spray coating, and other similar coating methods which are well known to those of ordinary skill in the art. Immersion coating and other coating techniques covering both sides of a substrate can also be used, or single-side coating techniques can be repeated on the other side of a substrate, if desired. These various application methods allow the coating to be placed on at least one side of the substrate in a range of thickness, thus enabling the coating of the invention to be appropriate for a variety of applications.
After the step of contacting, the coating composition and the substrate are subjected to solidification conditions which are sufficient to transpose and polymerize the coating composition so that the resulting solidified coating has a glass transition temperature of at least - 30 ° C. As used herein, the term "solidify" refers to the polymerization of the components of the composition. The coating composition and the substrate are normally heated to speed up the solidification of the coating composition. Temperatures in the range of about 50 ° C to about 110 ° C, for a period of time from about 2 to about 48 hours, can typically be used for most polymeric substrates. The preferred solidification conditions are temperatures in the range of about 60 ° C to about 90 ° C, for a period of time in the range of about 5 to about 18 hours.
The appropriate solidification conditions (ie, temperature and duration) will vary depending on the reactive nature of the components of the coating composition and the nature of the underlying substrate. In general, solidification conditions should be chosen so that the chosen substrate is not softened and distorted during solidification. However, certain materials may be able to withstand severe conditions. For example, if the substrate is glass, higher solidification temperatures and longer solidification times can be used. Also, when using compositions of the invention containing prepolymers, shorter solidification times are usually required. In general, when higher solidification temperatures are used to solidify the coating compositions of the present invention, shorter solidification times are required and vice versa.
Optionally, a presolidification step can be employed between the contact step and the solidification step. Pre-solidifying the coated substrate produces a coated surface free of asperities that can be handled for inspection or storage for the subsequent completion of the solidification process. The coated substrates are presolidified by exposing the substrate to lower temperatures and / or shorter times than those required for total solidification. The specific presolidification conditions (i.e., time / temperature) for a particular coating can be easily determined by those of ordinary skill in the art.
Prior to coating, the substrate surfaces can be prepared or otherwise treated to further promote adhesion and the formation of a continuous coating with the compositions of the invention. The preparation layer can also be used to impart additional properties to the solidified coating, such as, for example, impact resistance, light absorption, hardness and the like. The surfaces of the solid substrate can be prepared in a number of ways to alter the properties of the surface therein to promote the formation of a uniform coating. Said methods for preparing coating surfaces include chemical and physical methods that are well known to those skilled in the art. For example, the substrate can be etched chemically or physically or covered with a first layer.
As an alternative, the fluorinated polyurethane coatings of the present invention can be prepared as liners and sheets that are laminated to solid substrates. Thus, as used herein, the terms "liner" and "sheet" are used interchangeably with the term "coating". The liners and sheets can be prepared by methods such as liquid injection molding, casting and other similar methods that are well known to those of ordinary skill in the art. These liners and sheets can be laminated to the solid substrate by the use of an adhesive material, such as, for example, a liquid or solid film reactive or thermoplastic thermoset. The adhesive material is typically a transparent polymeric material, such as, for example, a polyurethane, an epoxy, an acrylate and the like.
Once solidified, the coatings of the present invention have a glass transition temperature (Tg) typically of at least -30 ° C. preferably, the glass transition temperature of the cured coating is at least 0 ° C, and more preferably, at least about 10 ° C.
The coating compositions of the present invention typically perform best when the thickness of the solidified coating is in the range of about 0.001 to about 0.050 inches. Preferably, the thickness of the solidified coating is in the range of about 0.002 to about 0.030 inches. More preferably, the thickness of the solidified coating is in the range of about 0.003 to about 0.020 inches.
The fluorinated polyurethane coatings of the present invention are trans-linked and typically have a molecular weight between branched points (MW branched point) of between about 200 and about 10,000 g / mole. Preferably, the solidified coatings of the present invention have a MW branched point of between about 500 and about 5,000 g / mole, and more preferably between about 500 and about 3,000 g / mole.
The fluorine content of the coatings of the invention can be adjusted by modifying the type and amount of the aliphatic fluorinated hydroxy functional compounds employed in the coating compositions of the present invention. As used herein, the term "fluorine content" refers to the percentage, based on weight, of fluorine atoms relative to the total weight of the solidified coating. The fluorine content of the coatings of the invention can be determined quantitatively using methods, such as ion chromatography, as well as other similar test methods for fluorine that are well known to those of ordinary skill in the art. The fluorine content of the solidified coatings of the present invention is typically less than about
80% by weight. Preferably, the fluorine content of the coatings of the invention is between about 0.1 and about 70 weight percent, and more preferably between about 0.1 and about 60 weight percent.
The fluorinated polyurethane coatings and liners of the present invention are remarkably transparent, thus overcoming a phenomenon typically found with fluorinated polyurethanes, ie, phase separation of fluorinated or non-fluorinated polyurethane precursor components in dispersing microdomains the light. As used herein, the term "polyurethane precursor" refers to an active compound that is capable of reacting with other compounds to form polyurethane. The phase separation during the polymerization usually causes the resulting fluorinated polyurethane coating or liner to be opaque. Thus, historically, fluorinated polyurethanes have not typically been suitable for use in applications where transparency and optical clarity are critical performance attributes.
In contrast, the fluorinated polyurethane coatings and liners of the present invention exhibit approximately the same degree of transparency as non-fluorinated polyurethane coatings. At least about 80% of incidental light is typically transmitted through the fluorinated polyurethane coatings of the invention (ie, 80% Light Transmission ("LT")), when measured through a stable film or through a coating on a transparent acrylic sheet substrate. The Light Transmission is measured according to ASTM DI 003, which is incorporated herein by reference. Preferably, the fluorinated polyurethane coatings and liners of the present invention exhibit a light transmission percentage of at least 85%. More preferably, the fluorinated polyurethane coatings and liners of the present invention exhibit a light transmission percentage of at least 90% LT.
The transparent fluorinated polyurethane coatings of the present invention are also very durable, as demonstrated by their relatively high tensile strength, tensile elongation and hardness. For example, the coatings of the invention typically exhibit a tensile strength of at least about 1000 psi. Preferably, the transparent coatings of the present invention exhibit a tensile strength of at least about 2000 psi, and more preferably a tensile strength of at least about 3000 psi.
The transparent coatings of the present invention typically exhibit a tensile elongation of at least about 50%. Preferably, the coatings of the invention exhibit a tensile elongation of at least about 100% and more preferably a tensile elongation of at least about 150%.
The coatings of the present invention typically exhibit a hardness, as measured by ASTM D2240, incorporated herein by reference, of at least about Shore A80 or Shore D30. Preferably, the transparent fluorinated polyurethane coatings of the present invention exhibit a hardness in the range of at least Shore A80 and around Shore D50 to about Shore D100, and more preferably in the range of about Shore D50 to about Shore D80.
The transparent fluorinated polyurethane coatings of the present invention typically exhibit a tearing strength of at least about 100 piw (inches per inch in width). Preferably, the clear solidified coatings of the present invention exhibit a tearing strength of at least about 300 piw. The tearing force can be measured according to ASTM D-624, which is incorporated herein by reference.
Significantly, the solidified coatings and liners of the present invention are not only transparent and mechanically durable, but also exhibit improved stability against the effects of weather compared to non-fluorinated polyurethane coatings. For example, surface cracks, roughness and yellowing, typically caused by molecular weight degradation, are reduced in the fluorinated polyurethane coatings and liners subject to weathering of the present invention, as compared to non-fluorinated polyurethane coatings subjected to weathering. .
In addition, compared to non-fluorinated polyurethane coatings, the fluorinated polyurethane coating surfaces of the present invention are stain resistant and easy to clean, exhibit higher water contact angles (resulting in a greater degree of water repellency and decreased ice adhesion), as well as superior chemical resistance to organic solvents and corrosive materials, such as, for example, acidic and basic materials.
In still another example of the present invention, articles are provided that are prepared in accordance with the methods of the present invention. The articles are generally solid transparent substrates or composites having a transparent, highly resistant, environmentally resistant, trans-entangled coating or liner of the present invention thereon.
The invention will be described below in greater detail with reference to the following non-limiting examples.
EXAMPLE 1 Preparation of a Non-Fluorinated Polyurethane Reference Polymer Coating (Composition 1) A reference coating of non-fluorinated polyurethane was prepared by the combination of a non-fluorinated polyol prepolymer and isocyanate, i.e., "Prepolymer 1" and a mixture of polyol, that is, "Polyol 1". Prepolymer 1 was made according to the following composition: Composition: Prepolymer 1 Weight% 4,4'-methylene-bis- (cyclohexyl isocyanate) 79.3 (Desmodur® W, Bayer, Pitsburgh, Pennsylvania)
Diol polycarprolactone 20.6 (H - (O - (CH 2) 5 - (OC) m - O - R - O - ((CO) (CH 2) 5 - Om - H, MW = 830 g / mole, - OH number 135) (Tone® 210, Union Carbide Corp., Danbury, Connecticut) Dibutyl Tin Dilaurate 0.01 (8% in 4,4'-methylene-bis- (cyclohexyl isocyanate) 100.0
The prepolymer 1 was prepared by the combination of 4,4'-methylene-bis- (cyclohexyl isocyanate), diol polycaprolactone and dibutyl tin dilaurate, then heating at 195 ° C for 2 hours, with stirring, under a nitrogen atmosphere. Polyol 1 was prepared by the combination of diol Tone and triol, 1,4-butanediol, UV stabilizer and antioxidant, in accordance with the following composition, then heating the mixture at 175 ° C for 2 hours with stirring.
Composition: Polyol 1 Weight% Triol polycaprolactone 84.1 (R - [O ((CO) (CH2) 5O) m - H] 3, MW = 540 g / mole, - OH number = 135) (Tone®, Union Carbide Corp. )
Diol Polycaprolactone 13.2 (H - (O - (CH 2) 5 - (PC)) m -O-R-O - ((CO) (CH 2) 5 -O) m-H); MW = 830 g / mole, - OH number = 135) Tone®-210, Union Carbide Corp.)
1,4 - Butanediol 0.7 UV Stabilizer 1.0 (Tinuvin®, Ciba Geigy AG) Antioxidant 1.0 (Irganox® 1076, Ciba Geigy AG) 100.0
A reference coating of non-fluorinated polyurethane was prepared by mixing Prepolymer 1, Polyol 1 and tin dilaurate dibutyl (in 4,4'-methyl ene-bis- (isocyanatocyclohexyl) in the amounts stated below, under vacuum to 105 ° F for 10 minutes, pouring the resulting solution on a glass platform After pouring, the solution was solidified at 180 ° C for 24 hours with a surface of the poured solution exposed to the air The resulting transparent solidified polyurethane sheet It was about 0.125 inches thick.
Composition Number 1: Non-Fluorinated Polyurethane Reference Weight (g) Prepolymer 1 1000 Polyol 1 1030 Tin dilaurate dibutyl 0.74 (8% in 4,4'-methylene-bis - (cyclohexyl isocyanate) 2030.74
This polyurethane sheet was characterized with respect to properties such as the percentage of light transmission (% LT), percentage of vagueness (% Hz), contact angle, hardness (Shore A or Shore D), tensile strength ( psi), glass transition temperature (Tg), and tearing strength (piw). The test methods are described in Tables I and II (Example 11).
EXAMPLE 2 Preparation of Fluorinated Polyurethane Coating Transparent Translayered from Prepolymer-based Compositions v Fluorinated Alcohol Based (Compositions numbers 2-4") The prepolymers from 2 to 4 were prepared from the following components:
The prepolymers 2, 3 and 4 were combined with Polyol 1 in the amounts provided below, then poured and solidified as described in Example 1.
The fluorinated polyurethane sheets were prepared by mixing the prepolymer (Prepolymer 2, 3 or 4), Polyol 1 and dibutyl tin dilaurate (in 4,4'-methylene-bis- (isocyanate cyclohexyl), under vacuum at 105 ° F. for 10 minutes, then pouring and solidifying each mixture, as described in Example 1.
Each of the resulting sheets was transparent. The properties of the sheets obtained from the compositions 2-4 are listed in Tables I and II (Example 11).
EXAMPLE 3 Preparation of a Non-Fluorinated Polyurethane Reference Coating and Transparent Trans-Linked Fluorinated Polyurethane Coating from a Fluoro-Sulfonamide-Based, Prepolymer-Based Alcohol-Based Composition (Compositions Nos. 5-6) Perfluorosulfonamide-based compositions were prepared as described in Example 2, except that different non-fluorinated polyols were used. The Prepolymers 5 and 6 were prepared from the following components:
"Polyol 2", a polyol-based prepolymer, was prepared according to the following composition:
Composition: Polyol 2 Weight% Triol polycaprolactone 53.4 (R - [O ((CO) (CH2) 5O) m - H] 3, MW = 300 g / mole, - OH number = 560) (Tone® 301, Union Carbide Corp .)
Diol Polycaprolactone 44.4 (H - (O - (CH 2) 5 - (OC)) m - O - R - O - ((CO) (CH 2) 5 - O) m - H); MW = 530 g / mole, - OH number = 212) Tone® - 200, Union Carbide Corp.)
UV Stabilizer 1.1 (Tinuvin®, Ciba Geigy AG)
Antioxidant 1.1 (Irganox® 1076, Ciba Geigy AG) 100.0 Polyol 2 was prepared by combining diol polycaprolactone and triol, UV stabilizer and antioxidant, then heating the mixture at 175 ° C for 2 hours with stirring.
A reference non-fluorinated polyurethane sheet and a fluorinated polyurethane sheet were prepared by combining the prepolymers 5 and 6, respectively, and Polyol 1 in the amounts described below, then pouring and heating the mixtures as described in Example 1.
After solidifying, both reference coatings of non-fluorinated polyurethane and fluorinated polyurethane of the present invention appeared clear.
The properties of the non-fluorinated reference coating and the fluorinated coating of the invention of this example are listed under Compositions numbers 5 and 6, in Tables I and II (Example 11).
EXAMPLE 4 Preparation of Transorbed Fluorinated Polyurethane Coatings
Transparent from Alcohol Based Compositions Fluoroalkane in a "One Step Method" (i.e., non-prepolymer based compositions) (Compositions numbers 7 and 8) The polyurethanes were prepared by a one step process using the following compositions:
The above components were mixed together at 180 ° F, degassed under vacuum, then poured into a mold made of two glass platforms with a peripheral seal. The mold was heated to 180 ° F for 234 hours to complete the solidification, which resulted in a 0.040-inch-thick fluorinated polyurethane sheet.
Both sheets of fluorinated polyurethane were transparent after solidifying.
The properties of the fluorinated polyurethane sheets prepared from the
Compositions numbers 7 and 8 are listed in Tables I and II (Example 11).
EXAMPLE 5 Preparation of Transparent Translucent Fluorinated Polyurethane Coatings from Polyol Fluoroalkane-based Compositions (Compositions No. 9) A reference coating of non-fluorinated polyurethane was prepared using a one-step process according to the following composition:
The above components were mixed at 180 ° F, degassed under vacuum, then poured into a mold made of two glass platforms with a peripheral seal. The mold was heated to 180 ° F for 24 hours to complete the solidification.
The resulting non-fluorinated polyurethane sheet was transparent. The properties of the solidified sheet obtained from Composition 9 are listed in Tables I and II (Example 11).
EXAMPLE 6 Preparation of Transparent Translucent Fluorinated Polyurethane Coatings from Polyol Fluoroalkane Based Compositions (Compositions No. 10-13) Polyurethanes were prepared by a one step process according to the following compositions:
The above components were mixed at 180 ° F, degassed under vacuum, then poured into a mold made of two glass platforms with a peripheral seal. The mold was heated at 180 ° C for 24 hours to complete the solidification.
The resulting fluorinated polyurethane sheets of the present invention were all transparent. The properties of these sheets are listed in Tables I and II (Example 11).
EXAMPLE 7 Preparation of Trans-Transparent Translucent Fluorinated Polyurethane Coatings from Polyol Fluoroalkane-based Compositions (Compositions No. 14-17) The fluorinated polyurethanes of the present invention were prepared as described in Example 6, except that the non-fluorinated polyols were replaced. in the coating composition. The compositions were the following:
The above components were mixed at 180 ° F, degassed under vacuum, then poured into a mold made of two glass platforms with a peripheral seal. The mold was heated at 180 ° C for 24 hours to complete the solidification.
The resulting fluorinated polyurethane sheets of the present invention were all transparent. The properties of these sheets are listed in Tables I and II (Example 11).
EXAMPLE 8 Preparation of Transorbed Fluorinated Polyurethane Coatings
Transparent from Polyol based compositions Fluoroalkane based on prepolymers (Compositions numbers 18 - 20) Fluorinated, trans-linked and transparent polyurethane coatings were prepared by combining a prepolymer based on perfluoro-1,10-decanediol, ie, the " Prepolymer 7"," Prepolymer 8"," Prepolymer 9"and Polyol 1. The Prepolymers 7-9 were prepared according to the following compositions:
100. 0 100.0 100.0
The fluorinated 7-9 Prepolymers were prepared by combining all the above components with stirring for 2 hours at 195 ° F under a nitrogen atmosphere. The Prepolymers 7-9 were then combined with the Polyol 1 in the amounts provided below, then poured and solidified as described in Example 1.
Each of the resulting fluorinated coatings of the invention was transparent. The properties of the coatings obtained from the compositions numbers 18-20 are listed in Tables I and II (Example 11).
EXAMPLE 9 Preparation of Trans-Transparent Translucent Fluorinated Polyurethane Coatings from a Prepolymer Based Fluoroether-Based Polyol Composition (Compositions Nos. 21 and 25) A transparent trans-entanted fluorinated polyurethane coating was prepared from a perfluoroether-based polyol prepolymer, i.e. , "Prepolymer 10", according to the following composition:
Composition: Prepolymer 10 Weight% Polyol perfluoroether 64.1 (HO - CH2CF2 - O - [(CF2) 2 - O] 6 - (CF2O) 6 - CF2CH2OH, MW = 935 g / mole, - OH number = 120) (Fluorobase® Z - 1030, Ausimont, SpA)
4,4'-methylene-bis- (cyclohexyl isocyanate) 35.9 (Desmodur® W, Bayer, Pitsburgh, Pennsylvania)
Dibutyl Tin Dilaurate 0.003 (8% in 4,4'-methylene-bis- (cyclohexyl isocyanate) 100.0
The prepolymer 10 was prepared by mixing the perfluoroether polyol and the isocyanate under nitrogen at 195 ° F. The dibutyl tin dilaurate was then added gradually to the mixture, with stirring, for a period of 1.5 hours. The prepolymer solution was stirred and heated for an additional hour at 195-200 ° F.
Transparent translucent fluorinated polyurethane liners were prepared according to the following compositions:
For each composition, the perfluoroether polyol and the trimethylol propane were combined and heated to 212 ° F under vacuum for 1.5 hours. The prepolymer 10 was heated in a separate container at 212 ° F, also under vacuum for 1.5 hours. All components were combined together, with stirring, then heated to 212 ° F under vacuum for 5 minutes. The solution was poured into a mold made of two glass platforms and a peripheral joint, then solidified at 275 ° F for 8 hours. The resulting transparent fluorinated polyurethane sheets each had 0.040 inches in thickness. The properties of these sheets are listed in Tables I and II (Example 11).
EXAMPLE 10 Test Methods I. Fluorine Content The fluorine content was calculated according to the following formula: [19 x number of fluorine atoms / Molecular Weight of the fluorinated polyol] x (% polyol fluorinated in polyurethane)
II. Molecular Weight between Branch Points The molecular weight between the branch points was calculated according to the following formula: 2 x total weight of polyurethane / total equivalents of triols
TU: Optical Clarity (Transmission) The percentage of light transmission was determined according to the standard test method ASTM D-1003, incorporated herein by reference.
TV. Hardness of Coating Hardness was determined according to the standard test method ASTM D-2240, incorporated herein by reference.
V. Tensile Force and Tension Elongation The tensile strength and the tensile elongation were determined in accordance with the standard test method ASTM D-638, incorporated herein by reference.
SAW. Water Contact Angle The water contact angles for the solidified coatings and liners of the invention were determined in accordance with ASTM standard test method D-724, incorporated herein by reference.
VII. Glass Transition Temperature (Tg) The glass transition temperatures for the solidified coatings and liners of the invention were determined in accordance with the standard test method ASTM D-5025, incorporated herein by reference.
VHI. Tearing Strength The tearing forces for the solidified coatings and liners of the invention were determined in accordance with the standard AST test method; D-624, incorporated herein by reference.
EXAMPLE 11 Characterization of the Fluorinated Polyurethane Coatings of the Invention The polyurethane coatings described in Examples 1 to 10 were characterized with respect to the attributes such as the percentage of light transmission, the vagueness percentage, the tensile strength, the tensile elongation, tearing force and contact angle to water according to the methods described in Example 12. The results are shown in Tables I and II, below.
The results of the test indicate that the fluorinated polyurethane coatings and liners of the present invention (preparations conforming to the compositions No. 2 -4, 6-8 and 10-24), are similar to non-fluorinated polyurethane coatings (prepared at starting from compositions numbers 1, 5 and 9), with respect to transparency and optical clarity (ie, the percentage of light transmission (% LT) and the percentage of vagueness (HZ) and mechanical force. they also demonstrate that the surface properties of the fluorinated polyurethane coatings and liners of the invention were significantly altered, as indicated by relatively higher water contact angles, compared to non-fluorinated polyurethane reference coatings. Water-to-water contact are related at the same time with improved water repellency and improved stain resistance.
They are also indicative of a surface rich in fluorine.
In addition to the tests described above, the chemical resistance of the coatings prepared from compositions number 1 (non-fluorinated composition) and 3 (a fluorinated composition of the present invention) was compared. The coated (and solidified) samples were exposed to 75% sulfuric acid for 10 minutes. After the exposure, the samples were washed with water and dried. The samples were evaluated for vagueness percentage according to ASTM D-1003. The results indicated that the vagueness of the non-fluorinated polyurethane coating (prepared from composition 1) had increased by 15% due to chemical attack. In contrast, the vagueness of the fluorinated polyurethane coating prepared in accordance with the present invention (ie, prepared from composition number 3) showed no change in vagueness. Accordingly, the fluorinated polyurethane coatings of the present invention exhibit marked improvement in chemical resistance compared to non-fluorinating polyurethane coatings.
The fluorinated polyurethane coatings of the present invention were also evaluated by degree of weather resistance, as compared to non-fluorinated coatings. The coatings prepared from composition numbers 1 and 5 (without fluorinating) and compositions numbers 2 and 6 (fluorinated polyurethane compositions of the present invention) were exposed in an accelerated weathering chamber QUV -B 313 (Q - Panel Co., Cleveland, Ohio) for 1000 hours in accordance with ASTM D - 4329. After exposure, the vagueness percentage of each of the samples was characterized as before. The vagueness values of the non-fluorinating polyurethane coatings prepared from compositions 1 and 5 were 4.1% and 18.6%, respectively. In contrast, the vagueness values for the fluorinated polyurethane coatings of the present invention prepared from compositions 2 and 6 were significantly lower in 0.9% and 1.2%, respectively. These results indicate that the fluorinated polyurethane coatings of the present invention are highly weather resistant, as compared to non-fluorinated polyurethane coatings.
A study was also carried out to determine the effect of increasing the degree of fluorination in coatings of the present invention. As shown in Tables I and II below, the increase in fluorine content to 47.84% in composition number 21 (fluorinated polyurethane coating prepared in accordance with the present invention) did not adversely affect transparency or optical clarity (% of light transmission) or the hardness of the coating of the invention.
The chemical resistance of the coatings of the invention is further improved by higher levels of fluorine. Coatings prepared from composition number 9 (non-fluorinated) and composition number 21 were conditioned at 120 ° F% 100% relative humidity for 2 days. A drop of 75% sulfuric acid was applied to each coating and allowed to stand under vacuum for 16 hours. The coatings were then exposed to -40 ° F for 8 hours, warmed to room temperature, then washed with cold water. Visual examination of the two coatings indicated that the coating prepared from composition number 1 had a white, opaque spot in the exposed area, while the coating prepared from composition number 21 was not affected. Accordingly, these results demonstrate that the fluorine content of the fluorinated polyurethane coatings of the invention can be varied widely without affecting optical clarity or environmental resistance.
TABLE I. Properties of Polyurethane Coatings (Examples 1 to 10)
TABLE L Properties of Polyurethane Coatings (Examples 1 to 10)
(- without measuring)
Claims (56)
- CF3 HO-CH2-CF2 -O- (CF2-CF-O) "-O-CF2CH2-OH wherein r is an integer chosen from 1 or 2, wherein n, m, p and q are chosen such that the molecular weight of the compounds encompassed by said formulas is between about 500 and about 5,000 g / mole, and wherein m / q is at least about 0.9; and wherein after application to a substrate and its subsequent solidification, said composition forms a translucent, transparent, weather resistant fluorinated polyurethane coating or liner having a glass transition temperature of at least about -30 ° C. .
- 2. The composition according to Claim 1, wherein said fluorinated aliphatic hydroxy functional compound has a molecular weight in the range of about 100 up to around 20,000 g / mole.
- 3. The composition according to Claim 2, wherein said fluorinated aliphatic hydroxy functional compound has a molecular weight in the range of from about 150 to about 10,000 g / mole.
- 4. The composition according to Claim 3, wherein said fluorinated aliphatic hydroxy functional compound has a molecular weight in the range of about 300 to about 5,000 g / mole.
- 5. The composition according to Claim 1, wherein said fluorinated alcohol is selected from the group consisting of a fluoroalkane alcohol, fluoroether alcohol, fluorosulfonamide alcohols and combinations of any two or more thereof.
- 6. The composition according to Claim 5, wherein said fluoroalkane alcohol has the formula, CF3 - (CF2) n - CH2CH2 - OH wherein n is a number in the range of about 1 to about 10.
- 7. The composition according to Claim 1, wherein said aliphatic fluorinated hydroxy functional compound is a fluoroalkane alcohol having the formula CF3 - (CF2) n - CH2CH2 - OH wherein n is a number in the range of about 3 to about 10
- 8. The composition according to Claim 5, wherein said fluoroether alcohol is selected from the group of compounds having the formula: CF3 CF3 -O- (CF2-CF-O) n -CH2-CH2-OH; CF3-O - [(CF2) 4-O-] "- CH2CH2-OH; CF3 CF3 - O - (CF2 CF - O -) ". CF2-O-) m CF2 CH2-OH; and mixtures thereof, wherein m and n are chosen independently of the numbers between about 1 to about 4.
- 9. The composition according to Claim 1, wherein said fluorinated aliphatic hydroxy functional compound is an alcohol fluoroether having the formula CF3 I CF 3 -O- (CF 2 CF -O-) 5 -CF 2 -O-) 3 CF 2 CH 2 -OH.
- 10. The composition according to Claim 5, wherein said fluorosulfonamide alcohol has the formula; R5-SO2-N-Re-OH I R7 wherein Rs is chosen from branched or straight chain optionally substituted fluorinated or partially fluorinated, alkyl, alkenyl or alkynyl radical having from about 1 to about 20 carbon atoms in the element principal, d is chosen from an optionally substituted fluorinated branched or straight chain, divalent alkyl, alkenyl or alkynyl radical having from about 1 to about 20 carbon atoms in the main element, and R7 is selected from a hydrogen atom, an optionally substituted, optionally fluorinated branched or straight chain, alkyl, alkenyl or alkynyl radical having from about 1 to about 20 carbon atoms in the main element.
- 11. The composition according to Claim 1, wherein said aliphatic fluorinated hydroxy functional compound is a fluorosulfonamide alcohol having the formula CF3 - (CF2) 7 - SO2 - N - (CH2) 2 - OH I (CH2CH3)
- 12. The composition according to Claim 1, wherein said fluoroalkane polyol is selected from the group consisting of compounds having the formulas: HO - (CH 2) n - (CF 2) m - (CH 2) P - OH; (HO - (CH2) n - CH - (CH2) m - (CF2) P - CF3; OH CF3 CF3 I I HO-CH2-CH2 - (CF-CF2) "- (CF2) m - (CF-CF2) P-CH2CH2-OH; and mixtures thereof, wherein m, n and p are chosen so that the molecular weight of the compounds encompassed by said formulas is between about 100 and about 2,000 g / mole.
- 13. The composition according to Claim 1, wherein said aliphatic fluorinated hydroxy functional compound is a fluoroalkane polyol selected from the group consisting of compounds having the formulas, HO-CH 2 - (CF 2) 4-CEU-OH, HO-CH 2 - ( CF2) 3-CH2-OH, and HO-CH2 - (CF2) 2 -CH2-OH (ie, the formula (X)); HO -CH2CH (OH) -CH2- (CF2) 5CF3) (i.e., 3-perfluorohexyl-propane-1-1,2-diol HO -CH2CH2 - (CF2) 5-CF (CF3) -CH2-CH2-OH .
- 14. The composition according to Claim 1, wherein said aliphatic fluorinated hydroxy functional compound is a perfluoroether polyol having the formula HO - (CH 2) rCF 2 --O - [(CF 2) nO] m - [(CF 2) pO] q - CF 2 (CH2) r-OH, wherein r is 1 or 2, wherein n, m, p and q are chosen so that the molecular weight of the compounds encompassed by said formulas is between about 500 and about 5,000 g / mole, and where m / q is at least about 1.0.
- 15. The composition according to Claim 1, wherein said aliphatic fluorinated hydroxy functional compound is a fluoroether polyol having the formula, HO - (CH2) rCF2 - O - [(CF2) 2O] 6 - [(CF2) pO] 6 - CF2 (CH2) r-OH.
- 16. The composition according to Claim 1, wherein the amount of the fluorinated hydroxy functional compound employed in said composition is between about 1 and about 85% by weight, based on the total weight of the composition.
- 17. The composition according to Claim 16, wherein the amount of the fluorinated hydroxy functional compound employed in said composition is between about 3 and about 70% by weight, based on the total weight of the composition.
- 18. The composition according to Claim 17, wherein the amount of the fluorinated hydroxy functional compound employed in said composition is between about 3 and about 60% by weight, based on the total weight of the composition.
- 19. The composition according to Claim 1, wherein said aliphatic polyisocyanate is selected from the group consisting of 4,4'-methylene-bis (cyclohexyl isocyanate), 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 1-4. - butane diisocyanate, 1,6-hexane diisocyanate, 1,10-decane diisocyanate, 2,2,4-trimethyl-1,6-hexano diisocyanate, bis - (3-methyl-4-isocyanato-cyclohexyl) methane, 2, 2-bis- (4-isocyanatocyclohexyl) propane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-dicyclohexyl diisocyanate, 2,4-dicyclohexyl diisocyanate and combinations of any two or more thereof.
- 20. The composition according to Claim 1, wherein the proportion of the -NCO- groups with the _OH groups in said composition is between about 1.5: 1 and about 1: 1.
- 21. The composition according to Claim 20, wherein the proportion of the -NCO- groups with the _OH groups in said composition is between about 1.1: 1 and about 1: 1.
- 22. The composition according to Claim 1, wherein the amount of aliphatic polyisocyanate in said composition is in the range of about 10 and about 60 weight percent, based on the total weight of the composition.
- 23. The composition according to Claim 22, wherein the amount of the aliphatic polyisocyanate in said composition is in the range of about 25 and about 50 percent by weight, based on the total weight of the composition.
- 24. The composition according to Claim 23, wherein the amount of the aliphatic polyisocyanate in said composition is in the range of about 35 and about 40 weight percent, based on the total weight of the composition.
- 25. The composition according to Claim 1, wherein said non-fluorinated polyol is selected from the group consisting of a monomeric polyol, a polymeric polyol and mixtures thereof.
- 26. The composition according to Claim 25, wherein said monomeric polyol is selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,12 - decanediol, 2,2-dimethyl-propane-1,3-diol, 1,4-cyclohexane-dimethylol, trimethylpropane and combinations of any two or more thereof.
- 27. The composition according to Claim 25, wherein said non-fluorinated polyol is selected from the group consisting of polyols polyether, polyols polyester, polycarbonate polyols and combinations of any two or more thereof.
- 28. The composition according to Claim 1, wherein said non-fluorinated polyol is trimethylpropane.
- 29. The composition according to Claim 1, wherein said polyol has a molecular weight in the range of from about 300 to about 5,000 g / mole.
- 30. The composition according to Claim 29, wherein said polyol has a molecular weight in the range of from about 500 to about 2,000 g / mole
- 31. The composition according to Claim 1, wherein the amount of said non-fluorinated polyol in said composition is between about 1 to about 90 percent by weight, based on the total weight of the composition.
- 32. The composition according to Claim 31, wherein the amount of said non-fluorinated polyol in said composition is between about 2 to about 80 percent by weight, based on the total weight of the composition.
- 33. The composition according to Claim 32, wherein the amount of said non-fluorinated polyol in said composition is between about 2 to about 70 percent by weight, based on the total weight of the composition.
- 34. The composition according to claim 1, further comprising a solidifying catalyst.
- 35. The composition according to Claim 1, wherein said aliphatic polyisocyanate and said non-fluorinated polyol are prepolymerized.
- 36. The composition according to Claim 1, wherein said aliphatic polyisocyanate and said fluorinated aliphatic hydroxy functional compound are preprolimerized.
- 37. The composition according to Claim 1, wherein said transparent and translucent fluorinated polyurethane coating has a glass transition temperature of at least about 0 ° C.
- 38. The composition according to Claim 1, wherein said transparent and translucent fluorinated polyurethane coating has a glass transition temperature of at least about 10 ° C.
- 39. The composition according to Claim 1, wherein said transparent and translucent fluorinated polyurethane coating has a molecular weight between branching points of between about 200 and about 10,000 g / mole.
- 40. The composition according to Claim 39, wherein said transparent and translucent fluorinated polyurethane coating has a molecular weight between branch points of between about 500 and about 5,000 g / mole.
- 41. The composition according to Claim 39, wherein said trans-entached and transparent fluorinated polyurethane coating has a molecular weight between branching points of between about 500 and about 3,000 g / mole.
- 42. The composition according to Claim 1, wherein said trans-entanced and transparent fluorinated polyurethane coating or sheath exhibits a degree of fluorination of less than about 80% by weight.
- 43. The composition according to Claim 42, wherein said trans-entanced and transparent fluorinated polyurethane coating or sheath exhibits a degree of fluorination of less than about 70% by weight.
- 44. The composition according to Claim 1, wherein said trans-entanced and transparent fluorinated polyurethane coating or sheath exhibits a degree of fluorination between about 0.1 and about 60% by weight.
- 45. The composition according to Claim 1, wherein said transparent and translucent fluorinated polyurethane coating or liner exhibits a light transmission percentage of at least about 80% LT.
- 46. The composition according to Claim 45, wherein said transparent and translucent fluorinated polyurethane coating or liner exhibits a light transmission percentage of at least about 85% LT.
- 47. The composition according to Claim 46, wherein said transparent and translucent fluorinated polyurethane coating or liner exhibits a light transmission percentage of at least about 90% LT.
- 48. The composition according to Claim 1, wherein said transparent and translucent fluorinated polyurethane coating or liner exhibits a tensile strength of at least about 1000 psi and a tensile elongation of at least about 50%.
- 49. The composition according to Claim 48, wherein said trans-entanced and transparent fluorinated polyurethane coating or sheath exhibits a tensile strength of at least about 2000 psi.
- 50. The composition according to Claim 49, wherein said trans-entangled and transparent fluorinated polyurethane coating or liner exhibits a tensile strength of at least about 3000 psi.
- 51. The composition according to Claim 1, wherein said trans-entanced and transparent fluorinated polyurethane coating exhibits a hardness of at least Shore D30 as measured by AST; D2240.
- 52. The composition according to Claim 51, wherein said hardness is in the range of about Shore D50 to about Shore D 100.
- 53. A method for coating a solid substrate comprising: (i) preparing a coated substrate by contacting a surface of a solid substrate with a coating composition of Claim 1; (ii) subjecting said coated substrate to solidification conditions such that said composition forms a transparent trans-entangled fluorinated polyurethane coating having a glass transition temperature of at least -30 ° C.
- 54. The method according to Claim 53, wherein said solidification conditions comprise heating said coated substrate to a temperature in the range of about 50 ° C to about 110 ° C, for a period of about 2 hours to about 48 hours. hours.
- 55. An article comprising a solid substrate having a transparent trans-entangled polyurethane coating or liner, prepared in accordance with the method of Claim 53.
- 56. The composition according to claim 1, wherein said composition is either free of solvents or substantially free of solvents. EXTRACT OF THE INVENTION In accordance with the present invention, coating compositions are provided for preparing trans-enameled fluorinated polyurethane coatings or liners exhibiting high optical clarity and transparency, as well as resistance to adverse environmental effects. The present invention also provides methods for coating solid substrates with transparent and environmentally resistant translucent fluorinated polyurethane coatings, as well as the resulting coated articles.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08828970 | 1997-03-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA99008718A true MXPA99008718A (en) | 2000-08-01 |
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