Weakly ionic aqueous suspensions of ground mineral matter and their uses

Abstract

The invention relates to the use of a weakly ionic and water-soluble copolymer as a grinding aid agent for grinding mineral matter in aqueous suspension in order to obtain aqueous suspensions of refined mineral matter, with a dry matter concentration that can be high, with a low Brookfield™ viscosity that remains stable over time, having the property that it presents a pigmentary surface area the ionic charge of which, as determined by ionic titration, is low. The invention relates to the aqueous suspensions of mineral matter obtained and their use in the fields of paper, paint and plastics.

1 - 33 . (canceled) 
   
   
       34 . An aqueous suspension of refined mineral matter comprising refined mineral matter and a grinding aid agent, wherein the grinding agent comprises a copolymer of:
 a) at least one ethylenically unsaturated anionic monomer having (i) a monocarboxyl function selected from ethylenically unsaturated monomers having a monocarboxyl function, or (ii) a dicarboxyl function selected from ethylenically unsaturated monomers having a dicarboxyl function or (iii) a sulfonic function selected from ethylenically unsaturated monomers having a sulfonic function, or (iv) a phosphoric function selected from ethylenically unsaturated monomers having a phosphoric function, or (v) a phosphonic function selected from ethylenically unsaturated monomers having a phosphonic function or mixtures thereof,   b) at least one non-ionic ethylenically unsaturated monomer of formula (I):   
     
       
         
         
             
             
         
       
     
     where
 m and p represent a number of alkylene oxide units less than or equal to 150, 
 n represents a number of ethylene oxide units less than or equal to 150, 
 q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150, 
 R 1  represents hydrogen or the methyl or ethyl radical, 
 R 2  represents hydrogen or the methyl or ethyl radical, 
 R represents a radical containing a polymerizable unsaturated function, 
 R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, 
 or a mixture of several monomers of formula (I), 
 c) at least one organofluorinated or organosilylated monomer selected from among the molecules of formulae (IIa) or (IIb) or (IIc) or mixtures thereof: 
 
     with formula (IIa) 
     
       
         
         
             
             
         
       
       where
 m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150, 
 n1 and n2 represent a number of ethylene oxide units less than or equal to 150, 
 q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150, 
 r represents a number such that 1≦r≦200, 
 R 3  represents a radical containing a polymerizable unsaturated function, 
 R 4 , R 5 , R 10  and R 11  represent hydrogen or the methyl or ethyl radical, 
 R 6 , R 7 , R 8  and R 9  represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof, 
 R 12  represents a hydrocarbon radical having from 1 to 40 carbon atoms, 
 A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms, 
 
     
     with formula (IIb)
   R-A-Si(OB) 3    
 where
 R represents a radical containing a polymerizable unsaturated function, 
 A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms, 
 B represents a hydrocarbon radical having from 1 to 4 carbon atoms, 
 
 
     with formula (IIc) 
     
       
         
         
             
             
         
       
       where
 m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150, 
 n3 and n4 represent a number of ethylene oxide units less than or equal to 150, 
 q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150, 
 r′ represents a number such that 1≦r′≦200, 
 R 13  represents a radical containing a polymerizable unsaturated function, 
 R 14 , R 15 , R 20  and R 21  represent hydrogen or the methyl or ethyl radical, 
 R 16 , R 17 , R 18  and R 19  represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof, 
 D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms, 
 
       d) optionally at least one monomer of the acrylamide or methacrylamide type or their derivatives or mixtures thereof, or at least one non water-soluble monomer, or at least one cationic monomer or quaternary ammonium, 
       e) optionally at least one crosslinking monomer selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, and allyl ethers prepared from polyols, 
     
     the total of the components a), b), c), d) and e) being equal to 100%, and having an intrinsic viscosity less than or equal to 100 ml/g determined in accordance with the method known as the intrinsic viscosity method. 
   
   
       35 . Paper, paint or plastic comprising a pigment prepared from the aqueous suspension of mineral matter according to  claim 34 . 
   
   
       36 . Paper comprising a pigment prepared from the aqueous suspension of mineral matter according to  claim 34 , wherein the pigment is included in the coating or surface treatment of the paper. 
   
   
       37 . Paper, board, or analogous sheets comprising a pigment prepared from the aqueous suspension of mineral matter according to  claim 34 , wherein the pigment is included as a filler in the paper, board or analogous sheets. 
   
   
       38 . Paper or board sheets comprising a pigment prepared from the aqueous suspension of mineral matter according to  claim 34 . 
   
   
       39 . Plastics comprising a pigment prepared from the aqueous suspension of mineral matter according to  claim 34 . 
   
   
       40 . A grinding aid agent for mineral matter in aqueous suspension, wherein the grinding agent comprises a copolymer of:
 a) at least one ethylenically unsaturated anionic monomer having (i) a monocarboxyl function selected from ethylenically unsaturated monomers having a monocarboxyl function, or (ii) a dicarboxyl function selected from ethylenically unsaturated monomers having a dicarboxyl function or (iii) a sulfonic function selected from ethylenically unsaturated monomers having a sulfonic function, or (iv) a phosphoric function selected from ethylenically unsaturated monomers having a phosphoric function, or (v) a phosphonic function selected from ethylenically unsaturated monomers having a phosphonic function, or mixtures thereof,   f) at least one non-ionic ethylenically unsaturated monomer of formula (I):   
     
       
         
         
             
             
         
       
     
     where
 m and p represent a number of alkylene oxide units less than or equal to 150, 
 n represents a number of ethylene oxide units less than or equal to 150, 
 q represents an integer equal to at least 1 and such that 5≦(m+n+p)q≦150, 
 R 1  represents hydrogen or the methyl or ethyl radical, 
 R 2  represents hydrogen or the methyl or ethyl radical, 
 R represents a radical containing a polymerizable unsaturated function, 
 R′ represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, 
 or a mixture of several monomers of formula (I), 
 g) at least one organofluorinated or organosilylated monomer selected from among the molecules of formulae (IIa) or (IIb) or (IIc) or mixtures thereof: 
 
     with formula (IIa) 
     
       
         
         
             
             
         
       
       where
 m1, p1, m2 and p2 represent a number of alkylene oxide units less than or equal to 150, 
 n1 and n2 represent a number of ethylene oxide units less than or equal to 150, 
 q1 and q2 represent an integer equal to at least 1 and such that 0≦(m1+n1+p1)q1≦150 and 0≦(m2+n2+p2)q2≦150, 
 r represents a number such that 1≦r≦200, 
 R 3  represents a radical containing a polymerizable unsaturated function, 
 R 4 , R 5 , R 10  and R 11  represent hydrogen or the methyl or ethyl radical, 
 R 6 , R 7 , R 8  and R 9  represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof, 
 R 12  represents a hydrocarbon radical having from 1 to 40 carbon atoms, 
 A and B are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms, 
 
     
     with formula (IIb)
   R-A-Si(OB) 3    
 where
 R represents a radical containing a polymerizable unsaturated function, 
 A is a group which may be present, in which case it represents a hydrocarbon radical having from 1 to 4 carbon atoms, 
 B represents a hydrocarbon radical having from 1 to 4 carbon atoms, 
 
 
     with formula (IIc) 
     
       
         
         
             
             
         
       
       where
 m3, p3, m4 and p4 represent a number of alkylene oxide units less than or equal to 150, 
 n3 and n4 represent a number of ethylene oxide units less than or equal to 150, 
 q3 and q4 represent an integer equal to at least 1 and such that 0≦(m3+n3+p3)q3≦150 and 0≦(m4+n4+p4)q4≦150, 
 r′ represents a number such that 1≦r′≦200, 
 R 13  represents a radical containing a polymerizable unsaturated function, 
 R 14 , R 15 , R 20  and R 21  represent hydrogen or the methyl or ethyl radical, 
 R 16 , R 17 , R 18  and R 19  represent straight or branched alkyl, aryl, alkylaryl or arylalkyl groups having from 1 to 20 carbon atoms, or a mixture thereof, 
 D and E are groups which may be present, in which case they represent a hydrocarbon radical having from 1 to 4 carbon atoms, 
 
       h) optionally at least one monomer of the acrylamide or methacrylamide type or their derivatives or mixtures thereof, or at least one non water-soluble monomer, or at least one cationic monomer or quaternary ammonium, 
       i) optionally at least one crosslinking monomer selected from the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, the allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, and allyl ethers prepared from polyols, 
     
     the total of the components a), b), c), d) and e) being equal to 100%, 
     and having an intrinsic viscosity less than or equal to 100 ml/g determined in accordance with the method known as the intrinsic viscosity method. 
   
   
       41 . A process for grinding mineral matter in aqueous suspension consisting of refining an aqueous suspension of said mineral materials into very fine particles characterized in that use is made, as a grinding aid agent before and/or during the grinding stage, of 0.05% to 10% by dry weight, with respect to the dry weight of mineral matter, of the copolymer according to  claim 40  and in that use may be made of at least one other dispersant or grinding aid agent before and/or during the grinding stage.