Polymer for masonry treatment and treating agent

Abstract

A treating agent containing a fluoropolymer for use in masonry treatment obtained from (A) a fluoromonomer, (B) a monomer having at least one acid group selected from the group consisting of carboxy, phosphate, phosphonate, phosphinate, sulfate, sulfo, and sulfino groups, and (C) a non-fluorinated monomer containing a hydrophobic group. The treating agent imparts to a masonry excellent water- and oil-repellency and excellent unsusceptibility to fouling.

1 . A fluorine-containing polymer for a masonry treatment, comprising: 
 (A) a fluorine-containing monomer,    (B) a monomer containing at least one acid group selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group and a sulfinic acid group, and    (C) a fluorine-free monomer containing a hydrophobic group.    
     
     
         2 . The fluorine-containing polymer according to  claim 1 , wherein the fluorine-containing monomer (A) is a monomer having: 
 at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group,    a fluoroalkenyl group and a fluoroether group, and    an unsaturated group of the formula: —O—CO—CX═CH 2      wherein X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2  group (in which X 1  and X 2  are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.    
     
     
         3 . The fluorine-containing polymer according to  claim 2 , wherein X is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2  group (in which X 1  and X 2  are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.  
     
     
         4 . The fluorine-containing polymer according to  claim 1 , wherein the hydrophobic group in the monomer (C) is a hydrocarbon group and/or a silicon-containing group.  
     
     
         5 . The fluorine-containing polymer according to  claim 4 , wherein the monomer (C) is a fluorine-free alkyl group-containing monomer and/or a polysiloxane group-containing monomer.  
     
     
         6 . The fluorine-containing polymer according to  claim 1 , wherein the acid group in the fluorine-containing group is in the form of a salt by adding a base as a neutralizing agent.  
     
     
         7 . The fluorine-containing polymer according to  claim 1 , which comprises: 
 (A) a fluorine-containing monomer having a fluorine-containing group, of the formula:                          wherein X is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2  group (in which X 1  and X 2  are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;    Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which optionally has an oxygen atom, an aromatic, cycloaliphatic or araliphatic group having 6 to 10 carbon atoms which optionally has an oxygen atom, a —CH 2 CH 2 N(R 1 )SO 2 — group (in which R 1  is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH(OY 1 )CH 2 — group (in which Y 1  is a hydrogen atom or an acetyl group); and    Rf is a linear or branched fluoroalkyl or fluoroalkenyl group having 1 to 21 carbon atoms, or a fluoroether group having totally 1 to 200 repeating units selected from the group consisting of the repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —CF 2 O—,    (B) a monomer containing at least one acid group selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group and a sulfinic acid group, and    (C) a fluorine-free monomer containing a hydrophobic group.    
     
     
         8 . The fluorine-containing polymer according to  claim 1 , which comprises: 
 (A) 35 to 90% by weight of a fluorine-containing monomer having a fluorine-containing group, of the formula:                          wherein X is a hydrogen atom or a methyl group;    Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which optionally has an oxygen atom, an aromatic, cycloaliphatic or araliphatic group having 6 to 10 carbon atoms which optionally has an oxygen atom, a —CH 2 CH 2 N(R 1 )SO 2 — group (in which R 1  is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH(OY 1 )CH 2 — group (in which Y 1  is a hydrogen atom or an acetyl group); and    Rf is a linear or branched fluoroalkyl or fluoroalkenyl group having 1 to 21 carbon atoms, or a fluoroether group having totally 1 to 200 repeating units selected from the group consisting of the repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —CF 2 O—,    (B) 5 to 50% by weight of a monomer containing at least one acid group selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group and a sulfuric acid group, and    (C) 2 to 18% by weight of a fluorine-free monomer containing a hydrophobic group, the % by weight is based on 100% by weight of the fluorine-containing polymer.    
     
     
         9 . The fluorine-containing polymer according to  claim 7 , wherein the carbon number of the Rf group is from 1 to 6.  
     
     
         10 . The fluorine-containing polymer according to  claim 9 , wherein the carbon number of the Rf group is from 1 to 4.  
     
     
         11 . A treatment agent for masonry comprising: 
 (1) the fluorine-containing polymer according to  claim 1 , and    (2) a liquid medium.    
     
     
         12 . The treatment agent according to  claim 11 , wherein the liquid medium is water and/or an organic solvent.  
     
     
         13 . The treatment agent according to  claim 11 , which further contains (3) a silicon-containing compound.  
     
     
         14 . A method of producing a masonry treatment agent which comprises preparing the fluorine-containing polymer according to  claim 1  by a solution polymerization, then adding a neutralizing agent and water to form a salt.  
     
     
         15 . A method of producing a masonry treatment agent which comprises preparing the fluorine-containing polymer according to  claim 1  by a solution polymerization, then removing the organic solvent before or after the addition of a neutralizing agent and water to form a salt.  
     
     
         16 . A method of treating masonry, comprising treating masonry with the treatment agent according to  claim 11 .  
     
     
         17 . The method according to  claim 16 , which comprises applying the treatment agent to masonry and then removing the liquid medium.  
     
     
         18 . A masonry produced by the method according to  claim 16.