Shoe uppers

Abstract

The present invention relates to an upper for a footwear article, said upper comprising at least one panel having at least one layer made from a composition comprising a fluorinated thermoplastic polyurethane polymer.

1 . An upper, for a footwear article, comprising at least one panel having at least one layer (E) made from a composition (C), wherein composition (C) comprises at least one F-TPU polymer, wherein F-TPU polymer is a fluorinated polyurethane comprising recurring units derived from:
 monomer (a), wherein monomer (a) is at least one diol selected from the group comprising poly-ether type diol, poly-ester type diol, polybutadien-diol and polycarbonate-diol;   monomer (b), wherein monomer (b) is at least one hydroxy-terminated (per)fluoropolyether polymer;   monomer (c), wherein monomer (c) is at least one aromatic, aliphatic or cycloaliphatic diisocyanate; and   monomer (d), wherein monomer (d) is at least one aliphatic, cycloaliphatic or aromatic diol having from 1 to 14 carbon atoms.   
     
     
         2 . The upper according to  claim 1 , wherein said at least one monomer (a) is selected from the group consisting of poly(ethylene)glycol, poly(propylene)glycol, poly(tetramethylen)glycol (PTMG), poly(1,4-butanediol)adipate, poly(ethandiol-1,4-butanediol) adipate, poly(1,6-hexandiol-neopentyl)glycol adipate, poly-caprolactone-diol (PCL) and polycarbonate-diol. 
     
     
         3 . The upper according to  claim 1 , wherein said at least one monomer (b) is a hydroxy-terminated (per)fluoropolyether polymer comprising a (per)fluoropolyoxyalkylene chain (R pf ) having two chain ends, wherein one or both chain ends terminates with at least one —OH group. 
     
     
         4 . The upper according to  claim 3 , wherein at least one chain end of said chain (R pf ) terminates with a group of formula (I):
   —CH 2 (OCH 2 CH 2 ) t —OH   (I)
   wherein   t is 0 or from 1 to 5.   
     
     
         5 . The upper according to  claim 3 , wherein both chain ends of said chain (R pf ) terminate with a group of formula (I):
   —CH 2 (OCH 2 CH 2 ) t —OH   (I)
   wherein   t is 0 or from 1 to 5.   
     
     
         6 . The upper according to  claim 3 , wherein said chain (R pf ) is a chain of formula
   —O-D-(CFX # ) z1 —O(R f )(CFX*) z2 -D*-O—
   wherein   z1 and z2, equal or different from each other, are equal to or greater than 1; X #  and X*, equal or different from each other, are —F or —CF3, provided that when z1 and/or z2 are greater than 1, X #  and X* are —F;   D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms; (R f ) comprises repeating units R o , said repeating units being independently selected from the group consisting of:   (i) —CFXO—, wherein X is F or CF 3 ;   (ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —F;   (iii) —CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, are F, Cl, or H;   (iv) —CF 2 CF 2 CF 2 CF 2 O—; and   (v) —(CF 2 ) j —CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula —O—R (f-a) -T, wherein R (f-a)  is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, and —CF 2 CF 2 CF 2 CF 2 O—, with each of each of X being independently F or CF 3  and T being a C 1 -C 3  perfluoroalkyl group.   
     
     
         7 . The upper according to  claim 6 , wherein said chain (R f ) is selected from the following formulae (R f -a) to (R f -c):
   —(CF 2 O) n (CF 2 CF 2 O) m (CF 2 CF 2 CF 2 O) p (CF 2 CF 2 CF 2 CF 2 O) q —  (R f -a)
   
       wherein m, n, p, q are 0 or integers selected in such a way as chain R f  meets the above number average molecular weight requirement, with the proviso that if p and q are simultaneously 0, n is not 0;
   —(CF 2 CF(CF 3 )O) a (CF 2 CF 2 O) b (CF 2 O) c (CF(CF 3 )O) d —  (R f -b)
 
 
       wherein a, b, c, d are 0 or integers selected in such a way as chain R f  meets the above number average molecular weight requirement; with the proviso that, at least one of a, c and d is not 0;
   —(CF 2 CF(CF 3 )O) e (CF 2 O) f (CF(CF 3 )O) g —  (R f -c)
 
 
       wherein e, f, g are 0 or integers selected in such a way as chain R f  meets the above number average molecular weight requirement. 
     
     
         8 . The upper according to  claim 1 , wherein said hydroxy-terminated (per)fluoropolyether polymer complies with the following formula (PFPE-I):
   HO—(CH 2 CH 2 O) t —CH 2 —(R pf )—CH 2 (OCH 2 CH 2 ) u —OH   (PFPE-I)
   wherein   t and u are, each independently, 0 or from 1 to 5; and   R pf  is a chain of formula
   —O-D-(CFX # ) z1 —O(R f )(CFX*) z2 -D*-O—
 
   wherein
 z1 and z2, equal or different from each other, are equal to or greater than 1, X #  and X*, equal or different from each other, are —F or —CF3, provided that when z1 and/or z2 are greater than 1, X #  and X* are —F; 
 D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 6 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms; 
 (R f ) comprises repeating units R o , said repeating units being independently selected from the group consisting of: 
 (i) —CFXO—, wherein X is F or CF 3 ; 
 (ii) —CFXCFXO—, wherein X, equal or different at each occurrence, is F or CF 3 , with the proviso that at least one of X is —F; 
 (iii) —CF 2 CF 2 CW 2 O—, wherein each of W, equal or different from each other, are F, Cl, or H; 
 (iv) —CF 2 CF 2 CF 2 CF 2 O—; and 
 (v) —(CF 2 ) j —CFZ—O— wherein j is an integer from 0 to 3 and Z is a group of general formula —O—R (f-a) -T, wherein R (f-a)  is a fluoropolyoxyalkene chain comprising a number of repeating units from 0 to 10, said recurring units being chosen from: —CFXO—, —CF 2 CFXO—, —CF 2 CF 2 CF 2 O—, and —CF 2 CF 2 CF 2 CF 2 O—, with each of each of X being independently F or CF 3  and T being a C 1 -C 3  perfluoroalkyl group. 
   
     
     
         9 . The upper according to  claim 1 , wherein said at least one monomer (c) is selected from the group consisting of 4,4-methylene-diphenylene-di-isocyanate (MDI), 1,6-hexan-diisocyanate (HDI), 2,4-toluene-diisocyanate, 2,6-toluene-diisocyanate, xylilen-diisocyanate, naphthalene-diisocyanate, paraphenylen-diisocyanate, hexamethylen-diisocyanate, isophorone-diisocyanate, 4,4-dicyclohexyl-methane-diisocyanate and cyclohexyl-1,4-diisocyanate. 
     
     
         10 . The upper according to  claim 1 , wherein said at least one monomer (d) is selected from the group consisting of ethylene-glycol, 1,4-butanediol (BDO), 1,6-hexane diol (HDO), N,N-diethanolamine and N,N-diisopropanolaniline. 
     
     
         11 . The upper according to  claim 1 , wherein at least 80% of blocks comprising recurring units derived from said monomer (b) are linked, on at least one of their ends, to a block comprising recurring units derived from said monomer (a) through a block comprising recurring units derived from said monomer (c). 
     
     
         12 . The upper according to  claim 1 , wherein said composition (C) is free of plasticizer agents. 
     
     
         13 . The upper according to  claim 1 , wherein said composition (C) comprises said F-TPU polymer in an amount of at least 60 wt. % based on the total weight of said composition (C). 
     
     
         14 . The upper according to  claim 1 , wherein said panel comprises layer E as outermost layer. 
     
     
         15 . A footwear article comprising an upper according to  claim 1 . 
     
     
         16 . The upper according to  claim 6 , wherein D and D*, equal or different from each other, are an alkylene chain comprising from 1 to 3 carbon atoms, said alkyl chain being optionally substituted with at least one perfluoroalkyl group comprising from 1 to 3 carbon atoms. 
     
     
         17 . The upper according to  claim 6 , wherein (R f ) consists of repeating units R o . 
     
     
         18 . The upper according to  claim 7 , wherein:
 when m is other than 0, the m/n ratio is between 0.1 and 20;   when (m+n) is other than 0, (p+q)/(m+n) is between 0 and 0.2;   when b is other than 0, a/b is between 0.1 and 10;   when (a+b) is different from 0, (c+d)/(a+b) is between 0.01 and 0.5; or   when e is other than 0, (f+g)/e is between 0.01 and 0.5.