(meth)acrylic copolymer, polymer solution, polymer-containing composition, anti-fouling coating composition, and method for producing (meth)acrylic copolymer

Abstract

First embodiment of a (meth)acrylic copolymer in the present invention includes following: a (meth)acrylic copolymer having at least one kind of constitutional unit selected from the group consisting of a constitutional unit (A1) having at least one kind of structure (I) selected from the group consisting of structures represented by the following formula (1), formula (2), or formula (3) and a constitutional unit (A2) having a triorganosilyloxycarbonyl group and a constitutional unit (B) derived from a macromonomer (b): (where, X represents —O—, —S—, or —NR 14 —, R 14 represents a hydrogen atom or an alkyl group, R 1 and R 2 each represent a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, R 3 and R 5 each represent an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, and R 4 and R 6 each represent an alkylene group having from 1 to 10 carbon atoms).

1 . A (meth)acrylic copolymer comprising:
 at least one kind of constitutional unit selected from the group consisting of a constitutional unit (A1) having at least one kind of structure (I) selected from the group consisting of structures represented by the following formula (1), formula (2), or formula (3) and a constitutional unit (A2) having a triorganosilyloxycarbonyl group; and   a constitutional unit (B) derived from a macromonomer (b):   
       
         
           
           
               
               
           
         
         (where, X represents —O—, —S—, or —NR 14 —, R 14  represents a hydrogen atom or an alkyl group, R 1  and R 2  each represent a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, R 3  and R 5  each represent an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, and R 4  and R 6  each represent an alkylene group having from 1 to 10 carbon atoms). 
       
     
     
         2 . A polymer solution comprising:
 a (meth)acrylic copolymer having a constitutional unit (A3) having at least one kind of structure (III) selected from the group consisting of structures represented by the following formula (4) or (5) and a constitutional unit (B) derived from a macromonomer (b); and   an organic solvent, wherein   a viscosity of the polymer solution at 25° C. is 5×10 4  mPa·s or less:
   —COO-M-OCO  (4)
 
   —COO-M-R 32   (5)
 
   (where, M represents Zn, Cu, Mg, or Ca and R 32  represents an organic acid residue other than a (meth)acryloyloxy group).   
     
     
         3 . A polymer-containing composition comprising the polymer solution according to  claim 2 , wherein
 a content of an organic solvent is 30% by mass or more with respect to a total amount of the polymer-containing composition excluding the (meth)acrylic copolymer.   
     
     
         4 . The polymer-containing composition according to  claim 3 , wherein a water content is 15% by mass or less. 
     
     
         5 . The (meth)acrylic copolymer according to  claim 1 , wherein the macromonomer (b) is a macromonomer having two or more constitutional units represented by the following formula (b′) and a number average molecular weight of from 500 to 50000: 
       
         
           
           
               
               
           
         
         (where, R 41  represents a hydrogen atom, a methyl group, or CH 2 OH and R 42  represents OR 43 , a halogen atom, COR 44 , COOR 45 , CN, CONR 46 R 47 , or R 48 , where R 43  to R 47  each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted nonaromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or substituted organosilyl group and R 48  represents an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group). 
       
     
     
         6 . The polymer solution according to  claim 2 , wherein the macromonomer (b) is a macromonomer having two or more constitutional units represented by the following formula (b′) and a number average molecular weight of from 500 to 50000: 
       
         
           
           
               
               
           
         
         (where, R 41  represents a hydrogen atom, a methyl group, or CH 2 OH and R 42  represents OR 43 , a halogen atom, COR 44 , COOR 45 , CN, CONR 46 R 47 , or R 48 , where R 43  to R 47  each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted nonaromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or substituted organosilyl group and R 48  represents an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group). 
       
     
     
         7 . The polymer-containing composition according to  claim 3 , wherein the macromonomer (b) is a macromonomer having two or more constitutional units represented by the following formula (b′) and a number average molecular weight of from 500 to 50000: 
       
         
           
           
               
               
           
         
         (where, R 41  represents a hydrogen atom, a methyl group, or CH 2 OH and R 42  represents OR 43 , a halogen atom, COR 44 , COOR 45 , CN, CONR 46 R 47 , or R 48 , where R 43  to R 47  each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heteroaryl group, an unsubstituted or substituted nonaromatic heterocyclic group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkaryl group, or an unsubstituted or substituted organosilyl group and R 48  represents an unsubstituted or substituted aryl group or an unsubstituted or substituted heteroaryl group). 
       
     
     
         8 . A polymer-containing composition comprising the (meth)acrylic copolymer according to  claim 1 . 
     
     
         9 . The polymer-containing composition according to  claim 8 , further comprising at least one kind of alkenyl compound selected from the group consisting of a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following formula (13), wherein
 the (meth)acrylic copolymer has the constitutional unit (A1):   
       
         
           
           
               
               
           
         
         (where, X represents —O—, —S—, or —NR 14 —, R 14  represents a hydrogen atom or an alkyl group, R 7  represents a hydrogen atom or an alkyl group having from 1 to 9 carbon atoms, R 8  represents a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, R 9  and R 11  each represent an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, R 10  represents a single bond or an alkylene group having from 1 to 9 carbon atoms, and R 12  represents an alkylene group having from 1 to 9 carbon atoms). 
       
     
     
         10 . An anti-fouling coating composition comprising the polymer-containing composition according to  claim 3 . 
     
     
         11 . The anti-fouling coating composition according to  claim 10 , further comprising an anti-fouling agent. 
     
     
         12 . The anti-fouling coating composition according to  claim 11 , wherein the anti-fouling agent contains at least one kind selected from the group consisting of cuprous oxide, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, pyridine-triphenylborane, and medetomidine. 
     
     
         13 . The anti-fouling coating composition according to  claim 10 , wherein a viscosity of the anti-fouling coating composition at 25° C. is 5000 mPa·s or less. 
     
     
         14 . The anti-fouling coating composition according to  claim 10 , wherein a VOC content is 500 g/L or less. 
     
     
         15 . The anti-fouling coating composition according to  claim 10 , further comprising a thermoplastic resin other than the (meth)acrylic copolymer. 
     
     
         16 . A method for producing a (meth)acrylic copolymer, the method comprising:
 a step of obtaining a (meth)acrylic copolymer by polymerizing a monomer mixture containing   at least one kind of monomer (a) selected from the group consisting of a monomer (a1) having at least one kind of structure (I) selected from the group consisting of structures represented by the following formula (1), formula (2), or formula (3), a monomer (a2) having triorganosilyloxycarbonyl group, and at least one kind of monomer (a3) selected from the group consisting of a monomer represented by the following formula (a3-1) and a monomer represented by the following formula (a3-2) and   a macromonomer (b):
                     
   (CH 2 ═C(R 31 )—CO—O) 2 M  (a3-1)
 
   CH 2 ═C(R 31 )—CO—O-M-R 32   (a3-2)
 
   (where, X represents —O—, —S—, or —NR 14 —, R 14  represents a hydrogen atom or an alkyl group, R 1  and R 2  each represent a hydrogen atom or an alkyl group having from 1 to 10 carbon atoms, R 3  and R 5  each represent an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group, R 4  and R 6  each represent an alkylene group having from 1 to 10 carbon atoms, M represents Zn, Cu, Mg, or Ca, R 31  represents a hydrogen atom or a methyl group, and R 32  represents an organic acid residue other than a (meth)acryloyloxy group).