Anti-soil silicone varnish compositions and support substrates treated therewith

Abstract

Silicone compositions, particularly for the production of anti-fouling varnishes which may be applied to flexible or bulk supports to provide an anti-fouling silicone varnish for textiles coated with elastomeric silicones which is economical, adhesive, low-slip and glossy; these are crosslinked silicone compositions comprising: A. at least one alkenylsilane, B. at least one catalytic system which comprises: B/1 at least one organometallic condensation catalyst, B/2 at least one metal M chelate and/or one metal alkoxide of general formula M(OJ) n , wherein n=valence of M and J=linear or branched C 1 -C 8 alkyl radical, M being selected from among: Ti, Zr, Ge and Al, C. at least one ultrafine filler, D. optionally, at least one arylsilane other than A. E. optionally, at least one other silane other than A. and other than D., F. optionally, at least one thickening agent and G. optionally, at least one functional additive.

1 . A silyl-containing varnish composition useful for providing anti-soil coatings, which comprises: 
 A. at least one alkenylsilane;    B. at least one catalytic system comprising: 
 B/1 at least one organometallic condensation catalyst;  
 B/2 at least one metal M chelate and/or at least one metal alkoxide of general formula M(OJ) n , wherein n=valence of M and J=linear or branched C 1 -C 8  alkyl radical, M being selected from the group consisting of Ti, Zr, Ge and Al;  
   C. at least one ultrafine filler;    D. optionally, at least one arylsilane other than A;    E. optionally, at least one other silane other than A and other than D;    F. optionally, at least one thickening agent; and    G. optionally, at least one functional additive.    
     
     
         2 . The varnish composition as defined by  claim 1 , said alkenylsilane A being selected from the group consisting of: 
 1. organoalkenylsilane monomer(s) comprising, per molecule, at least one alkenyl group;    2. the oligomers or condensates of said monomer(s) 1.;    3. the hydrolyzates obtained from said monomer(s) 1.; and    4. mixtures thereof.    
     
     
         3 . The varnish composition as defined by  claim 2 , said organoalkenylsilane monomer(s) comprising alkoxylated organoalkenylsilane(s).  
     
     
         4 . The varnish composition as defined by  claim 2 , said organoalkenylsilane monomer(s) having the general formula:  
       
         
           
           
               
               
           
         
       
       in which: 
 the radicals R 10 , R 20  and R 30 , which may be identical or different, are each hydrogen, or a hydrocarbon radical;  
 L is an alkylene radical;  
 L 1  is a valency bond or oxygen;  
 R 40  and R 50 , which may be identical or different, are each an alkyl radical;  
 x′=0 or 1;  
 x=0 to 2.  
 
     
     
         5 . The varnish composition as defined by  claim 2 , said monomers A1. comprising vinyl or allylalkoxysilanes or (meth)acryloyloxy(alkoxy)silanes.  
     
     
         6 . The varnish composition as defined by  claim 3 , comprising oligomers or condensates A2. obtained from vinyltrimethoxysilane (VTMO).  
     
     
         7 . The varnish composition as defined by  claim 2 , comprising a hydrolyzate A3. which comprises a mixture of at least one monomer A1. in acidic aqueous solution, the water/alkenylsilane monomer A1. molar ratio being less than or equal to 1.5.  
     
     
         8 . The varnish composition as defined by  claim 7 , said acidic aqueous solution comprising at least one acid selected from the group consisting of HCl, H 3 PO 4 , CH 3 COOH and mixtures thereof.  
     
     
         9 . The varnish composition as defined by  claim 2 , comprising from 20% to 60% by weight of oligomers or condensates A2. of said monomer(s) A1.  
     
     
         10 . The varnish composition as defined by  claim 1 , said at least one ultrafine filler C comprising inorganic fillers having a mean particle diameter Φme in the region of or less than 0.5 μm, and selected from the group consisting of siliceous fillers which comprise silica powders, colloidal silicas, combustion and precipitated silicas, or mixtures thereof, suspensions of nanometric fillers, other inorganic fillers which comprise TiO 2 , Al 2 O 3  mica, and mixtures thereof.  
     
     
         11 . The varnish composition as defined by  claim 1 , comprising at least one arylsilane D selected from the group consisting of phenyltrialkoxysilanes, phenylalkyldialkoxysilanes and mixtures thereof.  
     
     
         12 . The varnish composition as defined by  claim 1 , comprising at least one other silane E. selected from the group of the functionalized silanes comprising, per molecule, one or more functional groups which are identical to or different from one another and which are selected from the group consisting of the following functional groups: hydroxyl, amino (primary, secondary or tertiary amine, optionally included in a ring or in isocyanurate groups or HALS groups of the piperidine or other type), epoxy, (meth)acrylo and ureido.  
     
     
         13 . The varnish composition as defined by  claim 1 , crosslinkable by polycondensation and which comprises: 
 A. 100 parts by weight of alkenylsilane;    B. 0.1 to 10 parts by weight of a catalytic system comprising up to 80% by weight of organometallic condensation catalyst B/1;    C. 2 to 50 parts by weight of ultrafine filler;    D. 0 to 30 parts by weight of at least one arylsilane;    E. 0 to 30 parts by weight of at least one other silane other than A and D;    F. 0 to 3 parts by weight of at least one thickening agent;    G. 0 to 5 parts by weight of at least one functional additive.    
     
     
         14 . The varnish composition as defined by  claim 1 , having a dynamic viscosity η, expressed in mPa.s at 25° C. such that: 
 2≦η≦500.    
     
     
         15 . A process for varnishing a support substrate other than an architectural textile, comprising coating an anti-soil varnish composition as defined by  claim 1  onto a silicone face surface of a support substrate composed at least in part of a silicone.  
     
     
         16 . A process for varnishing a support substrate other than an architectural textile, comprising coating an anti-soil varnish composition as defined by  claim 1  onto a support substrate, the face surface of which comprises at least one nonsilicone (co)polymer.  
     
     
         17 . The process as defined by  claim 16 , said at least one nonsilicone (co)polymer comprising a polyamide, polyolefin, polyester, or blend or copolymer thereof.  
     
     
         18 . The process as defined by  claim 15 , comprising coating the support substrate with said varnish composition and then crosslinking the layer of varnish composition, optionally by thermally activating the crosslinking.  
     
     
         19 . The process as defined by  claim 15 , comprising coating said varnish composition onto said support substrate in an amount of less than or equal to 35 g/m 2 .  
     
     
         20 . A process for varnishing an architectural textile, comprising coating an anti-soil varnish composition as defined by  claim 1  onto a silicone surface of a support substrate composed at least in part of silicone.  
     
     
         21 . A process for varnishing an architectural textile, comprising coating on anti-soil varnish composition as defined by  claim 1  onto a support substrate, the face surface of which comprises at least one nonsilicone (co)polymer.  
     
     
         22 . The process as defined by  claim 21 , said at least one nonsilicone (co)polymer comprising a polyamide, polyolefin, polyester, or blend or copolymer thereof.  
     
     
         23 . The process as defined by  claim 20 , comprising coating the support substrate with said varnish composition and then crosslinking the layer of varnish composition, optionally by thermally activating the crosslinking.  
     
     
         24 . The process as defined by  claim 20 , comprising coating said varnish composition onto said support substrate in an amount of less than or equal to 35 g/m 2 .  
     
     
         25 . A composite which comprises a flexible support substrate selected from the group consisting of: 
 textiles,    nonwoven fibrous supports,    polymer films,    optionally, a coating integral with at least one of the face surfaces of the support substrate and comprising at least one layer of silicone elastomer and/or of at least one other (co)polymer, and at least one layer of varnish composition as defined by  claim 1 , in crosslinked state.    
     
     
         26 . A composite which comprises a bulk support substrate optionally shaped from silicone and/or at least partially coated with silicone, and at least one layer of varnish composition as defined by  claim 1 , in crosslinked state.  
     
     
         27 . The composite as defined by  claim 21  or  22 , said support substrate comprising at least one material selected from the group consisting of: 
 glass, in the massive form or in the form of fibers,    ceramics, in the massive form or in the form of fibers,    natural or synthetic polymers which are provided in the massive form, in the form of fibers or in the form of films,    cellulose or lignocellulose materials in the massive or fibrous form,    and combinations thereof.    
     
     
         28 . An architectural textile comprising a composite of a flexible support substrate selected from the group consisting of: 
 textiles,    nonwoven fibrous supports,    polymer films, optionally, a coating integral with at least one of the face surfaces of the support substrate and comprising at least one layer of silicone elastomer and of at least one other (co)polymer, and at least one layer of varnish composition as defined by  claim 1 , in crosslinked state.    
     
     
         29 . The architectural textile as defined by  claim 28 , said support substrate comprising at least one material selected from the group consisting of: 
 glass in the form of fibers,    ceramics in the form of fibers,    natural or synthetic polymers which are provided in the form of fibers or in the form of films,    cellulose or lignocellulose materials in the massive or fibrous form.