US 11,691,381 B2
Thermoformable beaded articles with removable stabilizing layer and methods thereof
Christopher B. Walker, Jr., St. Paul, MN (US); Matthew R. C. Atkinson, Grant, MN (US); Mary M. Caruso Dailey, Maplewood, MN (US); John C. Clark, Maplewood, MN (US); Vivek Krishnan, St. Paul, MN (US); Alexander J. Kugel, Woodbury, MN (US); Steven J. McMan, Stillwater, MN (US); and Abdullahi A. Mohamud, Minnetonka, MN (US)
Assigned to 3M innovative Properties Company, St. Paul, MN (US)
Appl. No. 16/336,999
Filed by 3M INNOVATIVE PROPERTIES COMPANY, St. Paul, MN (US)
PCT Filed Oct. 6, 2017, PCT No. PCT/US2017/055476
§ 371(c)(1), (2) Date Mar. 27, 2019,
PCT Pub. No. WO2018/075265, PCT Pub. Date Apr. 26, 2018.
Claims priority of provisional application 62/409,439, filed on Oct. 18, 2016.
Prior Publication US 2020/0031092 A1, Jan. 30, 2020
Int. Cl. B05D 3/06 (2006.01); B32B 5/16 (2006.01); B32B 5/22 (2006.01); B32B 7/06 (2019.01); D06P 1/52 (2006.01)
CPC B32B 5/16 (2013.01) [B32B 5/22 (2013.01); B05D 3/067 (2013.01); B32B 7/06 (2013.01); B32B 2274/00 (2013.01); B32B 2307/418 (2013.01); D06P 1/5285 (2013.01); Y10T 428/25 (2015.01)] 16 Claims
OG exemplary drawing
 
1. An article comprising:
(i) a bead film comprising a binder resin layer and a plurality of microspheres partially embedded to at least 60% of the microsphere diameter in the binder resin layer wherein a portion of the microspheres outwardly protrude a first distance from the surface of the binder resin layer;
(ii) a stabilizing layer disposed on the outwardly protruding microspheres opposite the binder resin layer, wherein the stabilizing layer intimately conforms to the protruding microspheres, and wherein the stabilizing layer has a glass transition temperature less than 100° C. and a storage modulus at 150° C. of at least 1.5 MPa wherein the stabilizing layer has a thickness greater than the first distance; and
(iii) a release agent, wherein (a) the binder resin layer comprises the release agent, (b) the stabilizing layer comprises the release agent, and/or (c) an intermediate layer comprises the release agent, wherein the intermediate layer is disposed between the plurality of microspheres and the stabilizing layer,
with the proviso that when a polymeric backbone of the binder resin layer has a fluorine content greater than 65 wt %, the stabilizing layer comprises a release agent selected from a silicone, a fluoropolymer, and combinations thereof, and wherein the article is not retroreflective.