| US 7,501,472 B2 | ||
| Aqueous fluoromodified polyurethane system for anti-graffiti and anti-soiling coatings | ||
| Norbert Steidl, Kienberg (Germany); Alois Maier, Engelsberg (Germany); Franz Wolfertstetter, Palling (Germany); Wolfgang Hiller, Tübingen (Germany); and Rupert Stadler, Mindelheim (Germany) | ||
| Assigned to Construction Research & Technology GmbH, Trostberg (Germany) | ||
| Appl. No. 10/485,617 PCT Filed Feb. 26, 2003, PCT No. PCT/EP03/01971 § 371(c)(1), (2), (4) Date Jan. 29, 2004, PCT Pub. No. WO03/072667, PCT Pub. Date Sep. 04, 2003. |
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| Claims priority of application No. 102 08 567 (DE), filed on Feb. 27, 2002. | ||
| Prior Publication US 2004/0192835 A1, Sep. 30, 2004 | ||
| This patent is subject to a terminal disclaimer. | ||
| Int. Cl. C08J 3/03 (2006.01); C08G 18/10 (2006.01); C08G 18/12 (2006.01); C08G 18/32 (2006.01); C09D 175/04 (2006.01) | ||
| U.S. Cl. 524—591 [524/839; 524/840; 528/49; 528/70; 528/71] | 29 Claims |
| 1. An aqueous fluoromodified polyurethane system for one- or two-component anti-graffiti and anti-soiling coatings, prepared
by the process comprising the steps of:
(a) preparing a binder component comprising an aqueous solution or dispersion of at least one of an optionally hydroxyl- or
amino-functional oligo- or polyurethane having fluorinated side chains, by
(a1) reacting from 2.5 to 12 parts by weight of a fluoromodifled polyol component (A)(i) having two or more isocyanate-reactive
hydroxyl groups and a molecular mass of from 500 to 2,000 daltons, wherein component (A)(i) is at least one of a reaction
product or a macromonomer of a monofunctional fluoroalcohol, an aliphatic diisocyanate, an aromatic diisocyanate, or both
an aliphatic diisocyanate and an aromatic diisocyanate, and a diethanolamine, wherein the fluoroalcohol is a perfluoroalkyl
alcohol having methylene groups of the formula
F(CF2)x—(CH2)y—OH
with x=4-20 and y=1-6
or hexafluoropropene oxide (HFPO) oligomer alcohol of the formula CF3CF2CF2O—(CF(CF3)CF2O)z—CF(CF3)CH2—OH,
wherein z is from 1 to 10
or a mixture thereof, from 10 to 50 parts by weight of a high molecular mass polyol component (A)(ii) having two or more polyisocyanate-reactive
hydroxyl groups and a molecular mass of from 500 to 6,000 daltons, and from 0 to 10 parts by weight of a low molecular mass
polyol component (A)(iii) having two or more polyisocyanate-reactive hydroxyl groups and a molecular mass of from 50 to 499
daltons with from 2 to 30 parts by weight of a polyisocyanate component (B) comprising at least one polyisocyanate having
two or more aliphatic or aromatic isocyanate groups or a paint polyisocyanate, and adding from 0 to 25 parts by weight of
a solvent component (C) composed of an inert organic solvent, optionally in the presence of a catalyst, to yield a polyurethane
preadduct;
(a2) reacting the polyurethane preadduct from stage (a1), optionally in the presence of a catalyst, with from 0.1 to 10 parts by weight of a low molecular mass, anionically modifiable
polyol component or polyamine component (A) (iv) having two or more polyisocyanate-reactive hydroxyl groups, amino groups
or a combination thereof and one or more inert carboxylic or sulfonic acid groups, some or all of which are optionally converted
by means of bases into at least one of carboxylate or sulfonate groups, respectively, or are already in the form of at least
one of carboxylate or sulfonate groups, having a molecular mass of from 100 to 1,000 daltons or with from 0.1 to 20 parts
by weight of a polymeric polyol component (A)(v) having two or more polyisocyanate-reactive hydroxyl groups and further, polyisocyanate-inert,
hydrophilic groups, having a molecular mass of from 500 to 5,000 daltons, to form a polyurethane prepolymer containing free
isocyanate groups;
(a3) optionally reacting the polyurethane prepolymer from stage (a2) such that some or all of the free isocyante groups are reacted with from 0.1 to 15 parts by weight of a chain terminator
component (D) having three or more isocyanato-reactive hydroxyl groups, primary amino groups, secondary amino groups, or a
combination thereof that react with the free isocyanate groups of the polyurethane prepolymer from stage (a2) and wherein component (D) has a molecular mass of from 50 to 500 daltons, to yield a polyfunctional polyurethane oligomer
or polymer that is chain terminated or partly chain terminated;
(a4) admixing the polyfunctional polyurethane oligomer or polymer that is chain terminated or partially chain terminated from
stage (a3) with from 0.1 to 10 parts by weight of a neutralizing component (E) to neutralize some or all of the acid groups to form
a neutralized polyurethane oligomer or polymer, and then
(a5) dispersing the neutralized polyurethane oligomer or polymer that is chain terminated or partially chain terminated from
stage (a4) in from 40 to 120 parts by weight of water to yield a dispersion of neutralized polyurethane oligomer or polymer, wherein
said dispersion of the neutralized polyurethane oligomer or polymer optionally contains from 0 to 50 parts by weight of a
formulating component (F), and
(a6) optionally reacting the neutralized polyurethane oligomer or polymer that is partially chain terminated from stage (a5) with from 0 to 10 parts by weight of a chain extender component (G) having three or more isocyanato-reactive primary amino
groups, secondary amino groups, or a combination thereof and a molecular mass of from 50 to 500 daltons, to yield a polyurethane
oligomer or polymer having at least one extended chain;
and, optionally,
(b) subsequently reacting the binder component prepared in stage (a5) or stage (a6) with from 20 to 100 parts by weight of a crosslinker component (H), wherein said crosslinker component (H) comprises a water-dispersible
polyisocyanate having at least two of an aliphatically, cycloaliphatically or aromatically attached isocyanate groups and
optionally containing from 0 to20 parts by weight of an organic solvent.
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