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 process for varnishing a support substrate other than an architectural textile, the process comprising:
 (a) forming a top coat layer of a varnish composition onto a surface of a support substrate comprising a silicone or silicone elastomer, wherein the varnish composition 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 formula M(OJ) n , wherein n=valence of M, J=linear or branched C 1 -C 8  alkyl radical, and M is selected from the group consisting of Ti, Zr, Ge and Al; 
 
 wherein said catalyst system comprises (B)/2 or a combination of (B)/1 and (B)/2; 
 (C) at least one ultrafine filler having a mean particle diameter of less than or equal to 0.5 μm; 
 (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; and 
   (b) cross-linking the top coat layer of the varnish composition to form an outer layer of cross-linked varnish on said substrate;   wherein the varnish composition forming the top coat layer has a dynamic viscosity η expressed in mPas·s at 25° C.) of between 2 and 500, inclusive.   
     
     
         2 . The process as defined by  claim 1 , wherein the at least one alkenylsilane is selected from the group consisting of:
 (a) organoalkenylsilane monomer(s) comprising, per molecule, at least one alkenyl group;   (b) the oligomers or condensates of said monomer(s) (a);   (c) the hydrolyzates obtained from said monomer(s) (a); and   (d) mixtures thereof.   
     
     
         3 . The process as defined by  claim 2 , wherein the organoalkenylsilane monomer is selected from the group consisting of vinyl alkoxysilanes, allylalkoxysilanes, (meth)acryloyloxy(alkoxy)silanes and an organoalkenylsilane monomer having the 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; and 
 x=0 to 2. 
 
       
     
     
         4 . The process as defined by  claim 1 , wherein at least one of the following conditions (a)-(c) is met:
 (a) said at least one ultrafine filler having a mean particle diameter of less than or equal to 0.5 μm is selected from the group consisting of siliceous fillers which comprise silica powders, colloidal silicas, combustion and precipitated silicas and mixtures thereof, suspensions of nanometric fillers, other inorganic fillers which comprise TiO 2 , Al 2 O 3  mica, and mixtures thereof;   (b) said at least one arylsilane other than (A) is selected from the group consisting of phenyltrialkoxysilanes, phenylalkyldialkoxysilanes and mixtures thereof; and   (c) said at least one other silane other than (A) and other than (D) is 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 and tertiary amine, optionally included in a ring, in isocyanurate groups and HALS groups of the piperidine and other type), epoxy, (meth)acrylo and ureido.   
     
     
         5 . A process for varnishing a support substrate other than an architectural textile, the process comprising:
 (a) forming a top coat layer of a varnish composition onto a surface of a support substrate comprising a silicone or silicone elastomer, wherein the varnish composition 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 formula M(OJ) n , wherein n=valence of M, J=linear or branched C 1 -C 8  alkyl radical, and M is selected from the group consisting of Ti, Zr, Ge and Al; 
 
 wherein said catalyst system comprises (B)/2 or a combination of (B)/1 and (B)/2; 
 (C) at least one ultrafine filler having a mean particle diameter of less than or equal to 0.5 μm; 
 (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; and 
   (b) cross-linking the top coat layer of the varnish composition to form an outer layer of cross-linked varnish on said substrate;   wherein the varnish composition forming the top coat layer has a dynamic viscosity η (expressed in MPas·s at 25° C.) of between 5 and 200, inclusive.   
     
     
         6 . The process as defined by  claim 5 , wherein the at least one alkenylsilane is selected from the group consisting of:
 (a) organoalkenylsilane monomer(s) comprising, per molecule, at least one alkenyl group;   (b) the oligomers or condensates of said monomer(s) (a);   (c) the hydrolyzates obtained from said monomer(s) (a); and   (d) mixtures thereof.   
     
     
         7 . The process as defined by  claim 6 , wherein the organoalkenylsilane monomer is selected from the group consisting of vinyl alkoxysilanes, allylalkoxysilanes, (meth)acryloyloxy(alkoxy)silanes and an organoalkenylsilane monomer having the 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; and 
 x=0 to 2. 
 
       
     
     
         8 . The process as defined by  claim 5 , wherein at least one of the following conditions (a)-(c) is met:
 (a) said at least one ultrafine filler having a mean particle diameter of less than or equal to 0.5 μm is selected from the group consisting of siliceous fillers which comprise silica powders, colloidal silicas, combustion and precipitated silicas and mixtures thereof, suspensions of nanometric fillers, other inorganic fillers which comprise TiO 2 , Al 2 O 3  mica, and mixtures thereof;   (b) said at least one arylsilane other than (A) is selected from the group consisting of phenyltrialkoxysilanes, phenylalkyldialkoxysilanes and mixtures thereof; and   (c) said at least one other silane other than (A) and other than (D) is 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 and tertiary amine, optionally included in a ring, in isocyanurate groups and HALS groups of the piperidine and other type), epoxy, (meth)acrylo and ureido.   
     
     
         9 . A process for varnishing a support substrate other than an architectural textile, the process comprising:
 (a) forming a top coat layer of a varnish composition onto a surface of a support substrate comprising a silicone or silicone elastomer, wherein the varnish composition 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 formula M(OJ) n , wherein n=valence of M, J=linear or branched C 1 -C 8  alkyl radical, and M is selected from the group consisting of Ti, Zr, Ge and Al; 
 
 Wherein said catalyst system comprises (B)/2 or a combination of (B)/1 and (B)/2; 
 (C) at least one ultrafine filler having a mean particle diameter of less than or equal to 0.5 μm; 
 (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; and 
   (b) cross-linking the top coat layer of the varnish composition to form an outer layer of cross-linked varnish on said substrate;   wherein the varnish composition forming the top coat layer has a dynamic viscosity η (expressed in MPas·s at 25° C.) of between 10 and 150, inclusive.   
     
     
         10 . The process as defined by  claim 9 , wherein the at least one alkenylsilane is selected from the group consisting of:
 (a) organoalkenylsilane monomer(s) comprising, per molecule, at least one alkenyl group;   (b) the oligomers or condensates of said monomer(s) (a);   (c) the hydrolyzates obtained from said monomer(s) (a); and   (d) mixtures thereof.   
     
     
         11 . The process as defined by  claim 10 , wherein the organoalkenylsilane monomer is selected from the group consisting of vinyl alkoxysilanes, allylalkoxysilanes, (meth)acryloyloxy(alkoxy)silanes and an organoalkenylsilane monomer having the 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; and 
 x=0 to 2. 
 
       
     
     
         12 . The process as defined by  claim 9 , wherein at least one of the following conditions (a)-(c) is met:
 (a) said at least one ultrafine filler having a mean particle diameter of less than or equal to 0.5 μm is selected from the group consisting of siliceous fillers which comprise silica powders, colloidal silicas, combustion and precipitated silicas and mixtures thereof, suspensions of nanometric fillers, other inorganic fillers which comprise TiO 2 , Al 2 O 3  mica, and mixtures thereof;   (b) said at least one arylsilane other than (A) is selected from the group consisting of phenyltrialkoxysilanes, phenylalkyldialkoxysilanes and mixtures thereof; and   (c) said at least one other silane other than (A) and other than (D) is 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 and tertiary amine, optionally included in a ring, in isocyanurate groups and HALS groups of the piperidine and other type), epoxy, (meth)acrylo and ureido.