Method for liquid proofing an item by plasma graft polymerisation

Abstract

A method for protecting an item from weight gain due to uptake of liquid comprising the step of exposing the item to plasma in a gaseous state for a sufficient period of time to allow a protective layer, particularly a polymeric layer, to be created on the surface of the item. Also encompassed is an item of footwear treated by the method.

1 . A method for protecting an item of footwear from weight gain due to uptake of liquid, the method comprising exposing the item, including any fasteners associated with the item, to a pulsed plasma in a gaseous state for a period sufficient to create a polymeric protective layer on the surface of the item and wherein the pulsed plasma comprises a compound selected from the group consisting of a compound of formula (V) 
       
         
           
           
               
               
           
         
         wherein R 8 , R 9 , R 10 , R 11 , R 12 , and R 13  independently are selected from hydrogen, halo, alkyl, haloalkyl or aryl optionally substituted by halo; and Z is a bridging group; 
         a compound of formula (VII) 
       
       
         
           
           
               
               
           
         
         where R 16 , R 17 , R 18 , R 19  and R 20  are independently selected from hydrogen, halogen, alkyl, haloalkyl or aryl optionally substituted by halo and R 21  is X—R 22  where R 22  is an alkyl or haloalkyl group and X is a bond, —C(O)O(CH 2 ) x Y— where x is an integer from 1 to 10 and Y is a bond or a sulphonamide group; or —(O) p R 23 (O) s (CH 2 ) t — where R 23  is aryl optionally substituted by halo, p is 0 or 1, s is 0 or 1 and t is 0 or an integer from 1 to 10, provided that where s is 1, t is other than 0; and 
         a compound of formula (VIII)
   R 24 —C≡C—X 1 —R 25   (VIII)
 
 
         where R 24  is hydrogen, alkyl, cycloalkyl, haloalkyl or aryl optionally substituted by halo; 
         X 1  is a bond or a bridging group; and R 25  is an alkyl, cycloalkyl or aryl group optionally substituted by halogen. 
       
     
     
         2 . The method of  claim 1 , wherein the fasteners are selected from laces and zippers. 
     
     
         3 . The method of  claim 2 , wherein the item is a sports shoe. 
     
     
         4 . The method of  claim 1 , wherein the item is exposed to the pulsed plasma within a plasma deposition chamber. 
     
     
         5 . The method of  claim 2 , wherein the exposing further comprises placing the item to be treated within a plasma chamber together with the selected one or more compounds, which are able to generate a target polymeric substance, in an essentially gaseous state; igniting a glow discharge within the chamber; and applying a suitable pulsed voltage. 
     
     
         6 . The method of  claim 5 , wherein the pulsed voltage is applied in a sequence in which the ratio of time on to time off is about 1:500 to about 1:1500. 
     
     
         7 . A method for protecting an item of footwear from weight gain due to uptake of liquid, the method comprising depositing by plasma polymerization deposition a repellent coating on the item, including any fasteners associated with the item, whereby the coating is deposited by plasma polymerization of one or more compounds selected from the group consisting of a compound of formula (V) 
       
         
           
           
               
               
           
         
         wherein R 8 , R 9 , R 10 , R 11 , R 12 , and R 13  independently are selected from hydrogen, halo, alkyl, haloalkyl or aryl optionally substituted by halo; and Z is a bridging group; 
         a compound of formula (VII) 
       
       
         
           
           
               
               
           
         
         wherein R 16 , R 17 , R 18 , R 19  and R 20  are independently selected from hydrogen, halogen, alkyl, haloalkyl or aryl optionally substituted by halo and R 21  is X—R 22  where R 22  is an alkyl or haloalkyl group and X is a bond, —C(O)O(CH 2 ) x Y— where x is an integer from 1 to 10 and Y is a bond or a sulphonamide group, or —(O) p R 23 (O) s (CH 2 ) t — where R 23  is aryl optionally substituted by halo, p is 0 or 1, s is 0 or 1 and t is 0 or an integer from 1 to 10, provided that where s is 1, t is other than 0; and 
         a compound of formula (VIII)
   R 24 —C≡C—X 1 —R 25   (VIII)
 
 
         wherein R 24  is hydrogen, alkyl, cycloalkyl, haloalkyl or aryl optionally substituted by halo, X 1  is a bond or a bridging group; and R 25  is an alkyl, cycloalkyl or aryl group optionally substituted by halogen. 
       
     
     
         8 . The method of  claim 7 , wherein the fasteners are selected from laces and zippers. 
     
     
         9 . The method of  claim 8 , wherein the item is a sports shoe. 
     
     
         10 . The method of  claim 7 , wherein the plasma deposition polymerization comprises a pulsed plasma. 
     
     
         11 . The method of  claim 10 , wherein the depositing further comprises placing the item to be treated within a plasma deposition chamber together with the one or more selected compounds, which are able to generate a target polymeric substance, in an essentially gaseous state, igniting a glow discharge within the chamber and applying a suitable voltage comprising a pulsed voltage. 
     
     
         12 . The method of  claim 11 , wherein the pulsed voltage is applied in a sequence in which the ratio of time on to time off is about 1:500 to about 1:1500. 
     
     
         13 . The method of  claim 7 , wherein the compound of formula (VIII) is a compound of formula (IX)
   CH≡C(CH 2 ) s —R 27   (IX)
   where s is 0 or an integer of 1 to 20 and R 27  is haloalkyl.   
     
     
         14 . The method of  claim 7 , wherein the compound of formula (VIII) is a compound of formula (X)
   CH≡C(O)O(CH 2 ) p R 27   (X)
   where p is an integer of 1 to 20 and R 27  is haloalkyl.   
     
     
         15 . An item of footwear protected from weight gain due to uptake of a liquid by applying the method of  claim 1 . 
     
     
         16 . An item of footwear protected from weight gain due to uptake of a liquid by applying the method of  claim 7 . 
     
     
         17 . A repellent coating that protects an item of footwear from weight gain due to uptake of liquid comprising a plasma-generated polymer created on the surface of the item, including any fasteners associated with the item, and substituents of the polymer comprise one or more compounds selected from the group consisting of a compound of formula (V) 
       
         
           
           
               
               
           
         
         wherein R 8 , R 9 , R 10 , R 11 , R 12 , and R 13  independently are selected from hydrogen, halo, alkyl, haloalkyl or aryl optionally substituted by halo; and Z is a bridging group; 
         a compound of formula (VII) 
       
       
         
           
           
               
               
           
         
         wherein R 16 , R 17 , R 18 , R 19  and R 20  are independently selected from hydrogen, halogen, alkyl, haloalkyl or aryl optionally substituted by halo and R 21  is X—R 22  where R 22  is an alkyl or haloalkyl group and X is a bond, —C(O)O(CH 2 ) x Y— where x is an integer from 1 to 10 and Y is a bond or a sulphonamide group, or —(O) p R 23 (O) s (CH 2 ) t — where R 23  is aryl optionally substituted by halo, p is 0 or 1, s is 0 or 1 and t is 0 or an integer from 1 to 10, provided that where s is 1, t is other than 0; and 
         a compound of formula (VIII)
   R 24 —C≡C—X 1 —R 25   (VIII)
 
 
         wherein R 24  is hydrogen, alkyl, cycloalkyl, haloalkyl or aryl optionally substituted by halo, X 1  is a bond or a bridging group; and R 25  is an alkyl, cycloalkyl or aryl group optionally substituted by halogen. 
       
     
     
         18 . The coating of  claim 17 , wherein the fasteners are selected from laces and zippers. 
     
     
         19 . The coating of  claim 18 , wherein the item is a sports shoe. 
     
     
         20 . The coating of  claim 17 , wherein the coating comprises a pulsed plasma-generated polymer.