Spill Resistant Surfaces Having Hydrophobic and Oleophobic Borders

Abstract

Described herein are methods for creating spill-proof or spill-resistant surfaces through the use of hydrophobic or oleophobic (H-SH) edges, borders and/or boundaries that contain the water and other liquids within the inside edges, borders and/or boundaries. Also described herein are spill-proof/spill-resistant surfaces. Liquid (e.g., water and other aqueous solutions/suspensions) heights of 3-6 mm on a level planar surface can be sustained by such edges, borders and/or boundaries. The H-SH borders can be created on glass, metal, wood, plastic, and concrete surfaces.

1 . A method for forming a spill-resistant border on a refrigeration shelf surface comprising activating a portion of the surface by etching or abrading it to form a roughened area on the surface and applying a composition to at least a portion of the roughened area on the surface that increases the hydrophobicity and oleophobicity of at least a portion of the roughened area on the surface that forms the spill-resistant border,
 wherein said spill-resistant border forms a perimeter around at least one area that has a lower hydrophobicity and lower oleophobicity than the spill-resistant border; and   wherein the composition comprises a silanizing agent that covalently binds the roughened area.   
     
     
         2 . The method of  claim 1 , further comprising applying a mask to said surface either before said activating, or said applying a composition, or before both activating a portion of the surface and applying the composition. 
     
     
         3 . The method of  claim 1 , wherein said activating comprises etching the surface with a chemical agent. 
     
     
         4 . The method of  claim 3 , wherein said chemical agent is hydrofluoric acid. 
     
     
         5 - 6 . (canceled) 
     
     
         7 . The method of  claim 2 , wherein said activating comprises abrading the surface. 
     
     
         8 - 12 . (canceled) 
     
     
         13 . The refrigerator shelf surface of  claim 47 , wherein said spill-resistant border provides a retention of up to 5.9 mm of water. 
     
     
         14 . The refrigerator shelf surface of  claim 47 , wherein said spill-resistant border provides a retention of up to 5.2 mm of a mixture comprising oil and water. 
     
     
         15 . The refrigerator shelf surface of  claim 47 , wherein said spill resistant border provides a retention of greater than 2.9 mm of water and less than 5.94 mm of water after four washings with soap and water. 
     
     
         16 - 26 . (canceled) 
     
     
         27 . The method of  claim 1 , wherein said composition comprises a silanizing agent having a terminal functionality that is selected from the group consisting of a fluoroalkyl or perfluoroalkyl. 
     
     
         28 . The method of  claim 27 , wherein said silanizing agent has at least one leaving group selected from the group consisting of chloro, —O-alkyl, —NH—(C 1 -C 6 alkyl), and —N—(C 1 -C 6 alkyl) 2 . 
     
     
         29 . The refrigerator shelf surface of  claim 15 , wherein said silanizing agent has at least one chloro leaving group. 
     
     
         30 . The refrigerator shelf surface of  claim 15 , wherein said silanizing agent, is a compound of formula (I):
   R 4-n Si—X n   (I)
   where n is an integer from 1-3;
 and wherein each R is independently selected from
 (i) alkyl or cycloalkyl group optionally substituted one or more fluorine atoms, 
 (ii) C 1 to 20  alkyl optionally substituted with one or more independently selected substituents selected from fluorine atoms and C 6-14  aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C 1 to 10  alkyl, C 1 to 10  haloalkyl, C 1 to 10  alkoxy, or C 1 to 10  haloalkoxy substituents, 
 (iii) C 6 to 20  alkyl ether optionally substituted with one or more substituents independently selected from fluorine and C 6-14  aryl groups, which aryl groups are optionally substituted with one or more independently selected halo, C 1 to 10  alkyl, C 1 to 10  haloalkyl, C 1 to 10  alkoxy, or C 1 to 10  haloalkoxy substituents, 
 (iv) C 6-14  aryl, optionally substituted with one or more substituents independently selected from halo or alkoxy, and haloalkoxy substituents; 
 (v) C 6 to 20  alkenyl or C 6 to 20  alkynyl, optionally substituted with one or more substituents independently selected from halo, alkoxy, or haloalkoxy[N]; and 
 (vi) —Z—((CF 2 ) q (CF 3 )) r , wherein Z is a C 1-12  divalent alkane radical or a C 2-12  divalent alkene or alkyne radical, and q is an integer from 1 to 12, and r is an integer from 1-4; 
 
 each X is independently selected from —H, —Cl, —I, —Br, —OH, —OR 2 , —NHR 3 , or —N(R 3 ) 2 ; 
 each R 2  is independently selected C 1 to 4  alkyl or haloalkyl group; and 
 each R 3  is independently selected C 1 to 4  alkyl or haloalkyl group. 
   
     
     
         31 . The method of  claim 30 , wherein R is a fluoroalkyl or perfluoroalkyl group comprising from 6 to 20 carbon atoms. 
     
     
         32 . The method of  claim 30 , wherein R is a fluoroalkyl or perfluoroalkyl group comprising from 8 to 20 carbon atoms. 
     
     
         33 - 46 . (canceled) 
     
     
         47 . A refrigerator shelf surface prepared by the method of  claim 1 . 
     
     
         48 - 49 . (canceled) 
     
     
         50 . A refrigerator shelf surface comprising a hydrophobic or oleophobic spill-resistant border, wherein said border comprises a roughened area covalently modified with a silanizing agent that forms a perimeter around at least one area that has a lower hydrophobicity and lower oleophobicity than said border; and 
       wherein said spill resistant border can withstand at least four washings with soap and water and still form a perimeter around at least one area that has a lower hydrophobicity and lower oleophobicity than said border. 
     
     
         51 - 57 . (canceled) 
     
     
         58 . The refrigerator shelf surface of  claim 50 , wherein said spill-resistant border provides a retention of up to 5.94 mm of water after four washings with soap and water. 
     
     
         59 . The refrigerator shelf surface of  claim 50 , wherein said spill-resistant border provides a retention of greater than 2.9 mm of water and less than 5.94 mm of water after four washings with soap and water. 
     
     
         60 - 94 . (canceled)