Siloxane composition not leasing hydrogen, intended for molding demoulding of tyres

Abstract

The present invention relates to a composition I, in the form of an oil-in-water emulsion, based on siloxane and which does not emit hydrogen, comprising: (a) optionally a nonreactive linear polyorganosiloxane oil with lubricating properties, (a′) a reactive linear polyorganosiloxane oil containing at least two OH groups per molecule, (b) a polyorganosiloxane resin, (c) a crosslinking agent which is soluble in the silicone phase comprising at least two functional groups capable of reacting with the polyorganosiloxane resin (b); (d) a condensation catalyst capable of catalyzing the reaction of the constituent (b) with the constituent (c); (e) a surfactant; and (f) water, (a) and (a′) being mixed together before emulsification, in an (a)/(a′) ratio of between 0 and 10.

1 - 32 . (canceled)  
     
     
         33 . A composition comprising: 
 (a) optionally, at least one nonreactive linear polyorganosiloxane oil having lubricating properties, having a dynamic viscosity of the order of 5×10 −2  to 30×10 2  Pa·s at 25° C. and consisting of a linear homopolymer or copolymer: 
 in which, per molecule, the monovalent organic substituents, which are identical to or different from each other, linked to the silicon atoms are selected from the group consisting of alkyl, cycloalkyl, alkenyl, aryl, alkylarylene and arylalkylene radicals,  
   (a′) at least one reactive linear polyorganosiloxane oil having at least two OH groups per molecule and having a dynamic viscosity ranging from 5×10 −2  to 200,000 Pa·s at 25° C.;    (b) at least one polyorganosiloxane resin carrying condensable hydroxyl substituents and having at least two different siloxyl units selected from those of the formula (R 1 ) 3 SiO 1/2  (M); (R 1 ) 2 SiO 2/2  (D); R 1 SiO 3/2  (T) and SiO 4/2  (Q), at least one of said units being a T or Q unit, in which formulae R 1  represents a monovalent organic substituent, the average number per molecule of organic radicals R 1  for a silicon atom being between 1 and 2;    (c) at least one crosslinking agent which is soluble in the silicone phase comprising at least two functional groups capable of reacting with the polyorganosiloxane resin (b);    (d) at least one condensation catalyst capable of catalyzing the reaction of the constituent (b) with the constituent (c);    (e) at least one surfactant; and    (f) water,    the quantities of surfactant(s) and of water being sufficient for producing an oil-in-water emulsion,    the constituent (a)/constituent (a′) weight ratio being within the range from 0 to 10, and the constituents (a), (a′), (b) and (c) being mixed with each other before emulsification    said composition being in the form of an oil-in-water emulsion which does not emit hydrogen.    
     
     
         34 . The composition according to  claim 33 , wherein the monovalent organic substituents specified in (a) are aryl, alkylarylene and/or arylalkylene radicals.  
     
     
         35 . The composition according to  claim 33 , wherein the dynamic viscosity specified in (a′) ranges from 5×10 −2  to 150,00 Pa·s at 25° C.  
     
     
         36 . The composition according to  claim 33 , wherein the dynamic viscosity specified in (a′) ranges from 5×10 −2  to 30×10 2  Pa·s at 25° C.  
     
     
         37 . The composition according to  claim 33 , wherein the resin (b) has a content by weight of hydroxyl substituents of between 0.1 and 10% by weight.  
     
     
         38 . The composition according to  claim 33 , wherein the resin (b) has a content by weight of hydroxyl substituents of between 0.2 and 5% by weight.  
     
     
         39 . The composition according to  claim 33 , wherein the constituent (a)/constituent (a′) weight ratio is within the range from 0 to 9.  
     
     
         40 . The composition according to  claim 33 , wherein the oil (a), when present, has per molecule at least 1 or 2% of aryl, alkylarylene and/or arylalkylene radicals.  
     
     
         41 . The composition according to  claim 33 , wherein the oil (a), when present, has per molecule from 5 to 50% of aryl, alkylarylene and/or arylalkylene radicals.  
     
     
         42 . The composition according to  claim 33 , wherein the oil (a), when present, has per molecule from 8 to 35% of aryl, alkylarylene and/or arylalkylene radicals.  
     
     
         43 . The composition according to  claim 33 , said composition comprising: 
 from 55 to 98.85 parts by weight of the sum of the constituents (a)+(a′);    from 1 to 30 parts by weight of the constituent (b),    from 0.1 to 10 parts by weight of the constituent (c),    from 0.05 to 5 parts by weight of the constituent (d),    per 100 parts by weight of the sum of the constituents (a)+(a′)+(b)+(c)+(d).    
     
     
         44 . The composition according to  claim 33 , wherein the oil (a), when it is present, comprises a linear polyorganosiloxane: 
 consisting along each chain: 
 of the units of formula R 2 R 3 SiO 2/2 , optionally combined with units of formula (R 2 ) 2 SiO 2/2 ,  
 of the units of formula (R 3 ) 2 SiO 2/2 , optionally combined with units of formula (R 2 ) 2 SiO 2/2 ,  
 of the units of formula R 2 R 3 SiO 2/2  and units of formula (R 3 ) 2 SiO 2/2 , optionally combined with units of formula (R 2 ) 2 SiO 2/2 ,  
   and blocked at each chain end with a unit of formula (R 4 ) 3 SiO 1/2  in which the radicals R 4 , which are identical or different, are selected from the radicals R 2  and R 3 ;    where the radicals R 2  and R 3 , monovalent organic substituents of the siloxyl units above, have the following definitions: 
 the radicals R 2 , which are identical to or different from each other, are selected from the group consisting of: linear and branched C 1 -C 6  alkyl radicals, C 3 -C 8  cycloalkyl radicals, and linear and branched C 2 -C 8  alkenyl radicals,  
 the radicals R 3 , which are identical to or different from each other, are selected from the group consisting of: C 6 -C 10  aryl radicals, C 6 -C 15  alkylarylene radicals, and C 6 -C 15  arylalkylene radicals; and  
   where at least 1 or 2%, in numerical terms, of the substituents R 2 , R 3  and R 4  are aromatic radicals R 3 .    
     
     
         45 . The composition according to  claim 44 , said composition comprising: 
 from 55 to 98.85 parts by weight of the sum of the constituents (a)+(a′);    from 1 to 30 parts by weight of the constituent (b),    from 0.1 to 10 parts by weight of the constituent (c),    from 0.05 to 5 parts by weight of the constituent (d),    per 100 parts by weight of the sum of the constituents (a)+(a′)+(b)+(c)+(d).    
     
     
         46 . The composition according to  claim 44 , wherein the radicals R 2 , which are identical to or different from each other, are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, vinyl and allyl; and wherein the radicals R 3 , which are identical to or different from each other, are selected from the group consisting of phenyl, naphthyl, tolyl, xylyl and benzyl.  
     
     
         47 . The composition according to  claim 44 , wherein from 5 to 50%, in numerical terms, of the substituents R 2 , R 3  and R 4  are aromatic radicals R 3 .  
     
     
         48 . The composition according to  claim 44 , wherein from 8 to 35%, in numerical terms, of the substituents R 2 , R 3  and R 4  are aromatic radicals R 3 .  
     
     
         49 . The composition according to  claim 44 , wherein the oil (a) comprises a linear polyorganosiloxane: 
 consisting along each chain: 
 of the units of formula R 2 R 3 SiO 2/2  combined with units of formula (R 2 ) 2 SiO 2/2 , of the units of formula (R 3 ) 2 SiO 2/2  combined with units of formula (R 2 ) 2 SiO 2/2 ;  
   and blocked at each chain end by a unit of formula (R 2 ) 3 SiO 1/2 ;    where the radicals R 2  and R 3  have the following definitions: 
 the radicals R 2 , which are identical to or different from each other, are selected from the group consisting of methyl, ethyl, propyl and isopropyl radicals, the radicals R 3 , which are identical to or different from each other, are selected from the group consisting of phenyl, tolyl and benzyl radicals; and  
   where at least 1 or 2%, in numerical terms, of the substituents R 2  and R 3  are phenyl, tolyl and/or benzyl radicals.    
     
     
         50 . The composition according to  claim 49 , wherein from 5 to 50%, in numerical terms, of the substituents R 2  and R 3  are phenyl, tolyl and/or benzyl radicals.  
     
     
         51 . The composition according to  claim 49 , wherein from 8 to 35%, in numerical terms, of the substituents R 2  and R 3  are phenyl, tolyl and/or benzyl radicals.  
     
     
         52 . The composition according to  claim 49 , wherein the oil (a) comprises a linear polyorganosiloxane having, per molecule, an aromatic substituents R 3 /Si ratio (in numerical terms) at least equal to 0.04.  
     
     
         53 . The composition according to  claim 52 , wherein the aromatic substituents R 3 /Si ratio (in numerical terms) ranges from 0.09 to 1.  
     
     
         54 . The composition according to  claim 53 , wherein the aromatic substituents R 3 /Si ratio (in numerical terms) ranges from 0.16 to 0.7.  
     
     
         55 . The composition according to  claim 33 , wherein the oil (a′) is a linear polyorganosiloxane oil carrying organic substituents selected from the group consisting of: 
 linear and branched alkyl radicals; linear and branched alkenyl radicals;    cycloalkyl and cycloalkenyl radicals; and cycloalkylalkylene and cycloalkenylalkylene radicals; said radicals being optionally substituted with —OH and/or amino and/or halogen and/or cyano groups.    
     
     
         56 . The composition according to  claim 44 , wherein the oil (a′) is a linear polyorganosiloxane oil carrying organic substituents selected from the group consisting of: 
 linear and branched alkyl radicals; linear and branched alkenyl radicals; cycloalkyl and cycloalkenyl radicals; and cycloalkylalkylene and cycloalkenylalkylene radicals; said radicals being optionally substituted with —OH and/or amino and/or halogen and/or cyano groups.    
     
     
         57 . The composition according to  claim 49 , wherein the oil (a′) is a linear polyorganosiloxane oil carrying organic substituents selected from the group consisting of: 
 linear and branched alkyl radicals; linear and branched alkenyl radicals;    cycloalkyl and cycloalkenyl radicals; and cycloalkylalkylene and cycloalkenylalkylene radicals; said radicals being optionally substituted with —OH and/or amino and/or halogen and/or cyano groups.    
     
     
         58 . The composition according to  claim 55 , wherein the oil (a′) has the formula  
       
         
           
           
               
               
           
         
       
       in which n is an integer greater than or equal to 10, R 5  and R 6 , which are identical or different, represent: (C 1 -C 6 )alkyl; (C 3 -C 8 )cycloalkyl; (C 2 -C 8 )alkenyl; or (C 5 -C 8 )cycloalkenyl; each of said radicals being optionally substituted with a halogen atom or a cyano residue.  
     
     
         59 . The composition according to  claim 56 , wherein the oil (a′) has the formula  
       
         
           
           
               
               
           
         
       
       in which n is an integer greater than or equal to 10, R 5  and R 6 , which are identical or different, represent: (C 1 -C 6 )alkyl; (C 3 -C 8 )cycloalkyl; (C 2 -C 8 )alkenyl; or (C 5 -C 8 )cycloalkenyl; each of said radicals being optionally substituted with a halogen atom or a cyano residue.  
     
     
         60 . The composition according to  claim 57 , wherein the oil (a′) has the formula  
       
         
           
           
               
               
           
         
       
       in which n is an integer greater than or equal to 10, R 5  and R 6 , which are identical or different, represent: (C 1 -C 6 )alkyl; (C 3 -C 8 )cycloalkyl; (C 2 -C 8 )alkenyl; or (C 5 -C 8 )cycloalkenyl; each of said radicals being optionally substituted with a halogen atom or a cyano residue.  
     
     
         61 . The composition according to  claim 58 , wherein R 5  and R 6  are selected independently from the group consisting of methyl, ethyl, propyl, isopropyl, cyclohexyl, vinyl and 3,3,3-trifluoropropyl.  
     
     
         62 . The composition according to  claim 59 , wherein R 5  and R 6  are selected independently from the group consisting of methyl, ethyl, propyl, isopropyl, cyclohexyl, vinyl and 3,3,3-trifluoropropyl.  
     
     
         63 . The composition according to  claim 60 , wherein R 5  and R 6  are selected independently from the group consisting of methyl, ethyl, propyl, isopropyl, cyclohexyl, vinyl and 3,3,3-trifluoropropyl.  
     
     
         64 . The composition according to  claim 61 , wherein 80% in numerical terms of said radicals are methyl radicals.  
     
     
         65 . The composition according to  claim 62 , wherein 80% in numerical terms of said radicals are methyl radicals.  
     
     
         66 . The composition according to  claim 63 , wherein 80% in numerical terms of said radicals are methyl radicals.  
     
     
         67 . The composition according to  claim 58 , wherein the oil (a′) is an α,ω-dihydroxypolydimethylsiloxane.  
     
     
         68 . The composition according to  claim 59 , wherein the oil (a′) is an α,ω-dihydroxypolydimethylsiloxane.  
     
     
         69 . The composition according to  claim 60 , wherein the oil (a′) is an α,ω-dihydroxypolydimethylsiloxane.  
     
     
         70 . The composition according to  claim 33 , wherein the oil (a), when it is present, and/or the oil (a′) has a dynamic viscosity at 25° C. of between 5×10 −2  and 30 Pa·s.  
     
     
         71 . The composition according to  claim 70 , wherein the oil (a), when it is present, has a dynamic viscosity at 25° C. of between 5×10 −2  and 5 Pa·s and the oil (a′) has a dynamic viscosity at 25° C. of between 0.1 and 5 Pa·s.  
     
     
         72 . The composition according  claim 33 , wherein the resin (b) is a hydroxylated DT or MDT resin comprising at least 20% by weight of T units and having a hydroxyl group content by weight ranging from 0.1 to 10%.  
     
     
         73 . The composition according to  claim 72 , wherein the hydroxyl group content by weight of said resin ranges from 0.2 to 5%.  
     
     
         74 . The composition according to  claim 33 , wherein the resin (b) has a dynamic viscosity at 25° C. of between 0.2 and 200 Pa·s.  
     
     
         75 . The composition according to  claim 72 , wherein the resin (b) has a dynamic viscosity at 25° C. of between 0.2 and 200 Pa·s.  
     
     
         76 . The composition according to  claim 74 , wherein the resin (b) has a dynamic viscosity at 25° C. of between 0.5 and 50 Pa·s.  
     
     
         77 . The composition according to  claim 75 , wherein the resin (b) has a dynamic viscosity at 25° C. of between 0.5 and 50 Pa·s.  
     
     
         78 . The composition according to  claim 76 , wherein the resin (b) has a dynamic viscosity at 25° C. of between 0.8 and 5 Pa·s.  
     
     
         79 . The composition according to  claim 77 , wherein the resin (b) has a dynamic viscosity at 25° C. of between 0.8 and 5 Pa·s.  
     
     
         80 . The composition according to  claim 33 , wherein the constituent (c) is a crosslinking agent of the formula:  
         Y a Si(Zi) 4-a    in which: 
 a is 0, 1 or 2;  
 Y is a monovalent organic group; and  
 the groups Zi, which are identical or different, are selected from the group consisting of: —OX a ,  
                     
 and —O—N═CX 1 X 2 , in which X a , X b , X 1  and X 2  are independently linear or branched C 1 -C 10  alkyl radicals; X 1  and X 2  may additionally represent hydrogen; and X a  is a radical which is optionally substituted with (C 1 -C 3 )alkoxy.  
   
     
     
         81 . The composition according to  claim 80 , wherein the constituent (c) is an alkyltrialkoxysilane of formula YSiZ 3  in which Y is alkyl, and Z is alkoxy.  
     
     
         82 . The composition according to  claim 81 , wherein the constituent (c) is selected from the group consisting of organotrialkoxysilanes, organotriacyloxysilanes, organotrioximosilanes and tetraalkyl silicates.  
     
     
         83 . The composition according to  claim 33 , further comprising (g) from 0.5 to 15 parts by weight, per hundred parts by weight of the sum of the constituents (a)+(a′)+(b)+(c)+(d)+(g), of a water-soluble crosslinking agent which is a silane carrying at least one organic group with a functional group F r , F r  being selected from the group consisting of optionally substituted amino functional groups, epoxy functional groups, optionally substituted acroyl (CH 2 ═CH—CO) functional groups, optionally substituted methacroyl (CH 2 ═C(CH 3 )—CO—) functional groups, optionally substituted ureido (NH 2 —CO—NH—) functional groups, optionally substituted thiol functional groups and a halogen atom.  
     
     
         84 . The composition according to  claim 83 , wherein the constituent (g) has the formula R 2 R 1 N—R a —Si(OH) 3  in which R a  represents alkylene and R 1  and R 2  represent a hydrogen atom or an alkyl group.  
     
     
         85 . The composition according to  claim 33 , further comprising a film-forming polymer.  
     
     
         86 . The composition according to  claim 85 , wherein the film-forming polymer is a styrene-acrylic polymer.  
     
     
         87 . The composition according to  claim 33 , comprising from 40 to 95% by weight of water.  
     
     
         88 . The composition according to  claim 33 , comprising from 0.5 to 10% by weight of surfactant.  
     
     
         89 . The composition according to  claim 33 , wherein the constituent (a)/constituent (a′) weight ratio is in the range from 1.5 to 10.  
     
     
         90 . The composition according to  claim 89 , wherein the constituent (a)/constituent (a′) weight ratio is in the range from 1.5 to 9.  
     
     
         91 . The composition according to  claim 90 , wherein the constituent (a)/constituent (a′) weight ratio is in the range from 2 to 6.  
     
     
         92 . The composition according to  claim 91 , wherein the constituent (a)/constituent (a′) weight ratio is in the range from 3 to 5.  
     
     
         93 . The composition according to  claim 92 , wherein the constituent (a)/constituent (a′) weight ratio is in the range from 3.5 to 4.5.  
     
     
         94 . The composition according to  claim 33 , wherein the constituent (a)/constituent (a′) weight ratio is equal to 0.  
     
     
         95 . The composition according to  claim 33 , wherein the constituent (a)/constituent (a′) weight ratio is in the range from 0 to 1.  
     
     
         96 . An article coated with a composition according to  claim 33 .  
     
     
         97 . An article obtained by heating an article according to  claim 96 .  
     
     
         98 . An inflatable rubber bladder coated on its outer surface with a composition according to  claim 33 , suitable for forming and curing pneumatic or semi-pneumatic tires.  
     
     
         99 . An inflatable rubber bladder obtained by heating a bladder according to  claim 98  to a temperature of 80 to 150° C.  
     
     
         100 . A raw pneumatic or semipneumatic tire having components which will constitute its outer tread for coming into contact with the ground, coated on its inner surface with a composition according to  claim 89 .  
     
     
         101 . A method for the lubrication of an article comprising applying thereto a lubricating composition according to  claim 89 .  
     
     
         102 . A method for lubricating an inflatable curing bladder comprising applying a lubricating composition according to  claim 89  to said inflatable bladder during the forming and curing of pneumatic or semipneumatic tires.  
     
     
         103 . A method for priming the bonding of an inflatable bladder comprising applying a composition according to  claim 94  to said inflatable bladder as a bonding primer.  
     
     
         104 . A method for priming the bonding of an inflatable bladder comprising applying a composition according to  claim 95  to said inflatable bladder as a bonding primer.