Graft copolymer, crosslinked particles, graft crosslinked particles, rubbery polymer, and thermoplastic resin composition using same

Abstract

Provided is a graft copolymer that has an excellent impact-resistance-imparting effect and that can provide a thermoplastic resin composition excellent in weather resistance and color developability. A graft copolymer (C) obtained by graft-polymerizing one or two or more monomers (B), which are selected from (meth)acrylic acid esters, aromatic vinyls, vinyl cyanides, N-substituted maleimides, and maleic acid, onto a composite rubber-like polymer (A), which is obtained by polymerizing a mixture (Ac) containing a polyorganosiloxane (Aa) and an acrylic acid ester (Ab) after forming a miniemulsion in water solvent. A thermoplastic resin composition that contains the graft copolymer (C) and a thermoplastic resin (D).

1 . A graft copolymer (C) obtained by graft-polymerizing one or two or more monomers (B), which are selected from (meth)acrylic acid esters, aromatic vinyls, vinyl cyanides, N-substituted maleimides, and maleic acid, onto a composite rubber-like polymer (A), which is obtained by polymerizing a mixture (Ac) containing a polyorganosiloxane (Aa) and an acrylic acid ester (Ab) after forming a miniemulsion in water solvent. 
     
     
         2 . (canceled) 
     
     
         3 . (canceled) 
     
     
         4 . (canceled) 
     
     
         5 . A thermoplastic resin composition comprising: the graft copolymer (C) according to  claim 1 ; and a thermoplastic resin (D). 
     
     
         6 . (canceled) 
     
     
         7 . A molded article obtained by molding the thermoplastic resin composition according to  claim 5 . 
     
     
         8 . Crosslinked particles (A-I) obtained by polymerizing a monomer mixture (i-I) containing a di(meth)acrylic acid ester (a) having a number average molecular weight (Mn) of 800 to 9,000 and represented by formula (1): 
       
         
           
           
               
               
           
         
         wherein X represents a divalent residue constituted by at least one diol selected from polyalkylene glycols, polyester diols, and polycarbonate diols, and R 1a  and R 1b  each independently represent H or CH 3 . 
       
     
     
         9 . (canceled) 
     
     
         10 . (canceled) 
     
     
         11 . The crosslinked particles (A-I) according to  claim 8 , wherein the monomer mixture (i-I) contains the di(meth)acrylic acid ester (a), an aromatic vinyl (b), and a vinyl cyanide (c), and a proportion of the aromatic vinyl (b) in 100% by mass of a total of the aromatic vinyl (b) and the vinyl cyanide (c) is 60% to 90% by mass. 
     
     
         12 . (canceled) 
     
     
         13 . (canceled) 
     
     
         14 . Graft crosslinked particles (B-I) obtained by graft-polymerizing a monomer onto the crosslinked particles (A-I) according to  claim 8 . 
     
     
         15 . (canceled) 
     
     
         16 . (canceled) 
     
     
         17 . A thermoplastic resin composition comprising: the crosslinked particles (A-I) according to  claim 8  and a thermoplastic resin (D-I). 
     
     
         18 . A molded article obtained by molding the thermoplastic resin composition according to  claim 17 . 
     
     
         19 . Crosslinked particles (A-II) having a volume average particle size of 0.07 to 2.0 μm and obtained by polymerizing a monomer mixture (i-II) containing a di(meth)acrylic acid ester (a) and a mono(meth)acrylic acid component (d), wherein a content of the di(meth)acrylic acid ester (a) in 100% by mass of the monomer mixture (i-II) is 20% to 80% by mass, the di(meth)acrylic acid ester (a) having a number average molecular weight of 800 to 9,000 and being represented by formula (1): 
       
         
           
           
               
               
           
         
         wherein X represents a divalent residue constituted by at least one diol selected from polyalkylene glycols, polyester diols, and polycarbonate diols, and R 1a  and R 1b  each independently represent H or CH 3 . 
       
     
     
         20 . (canceled) 
     
     
         21 . (canceled) 
     
     
         22 . (canceled) 
     
     
         23 . (canceled) 
     
     
         24 . Graft crosslinked particles (B-II) obtained by graft-polymerizing one or more monomers selected from (meth)acrylic acid esters, aromatic vinyls, vinyl cyanides, maleimides, and maleic anhydride onto the crosslinked particles (A-II) according to  claim 19 . 
     
     
         25 . (canceled) 
     
     
         26 . (canceled) 
     
     
         27 . A thermoplastic resin composition comprising: the crosslinked particles (A-II) according to  claim 19  and a thermoplastic resin (D-II). 
     
     
         28 . A molded article obtained by molding the thermoplastic resin composition according to  claim 27 . 
     
     
         29 . A rubbery polymer (A-III) that is a miniemulsion polymerization reaction product of an alkyl (meth)acrylate. 
     
     
         30 . The rubbery polymer (A-III) according to  claim 29 , wherein the rubbery polymer (A-III) is a miniemulsion polymerization reaction product of a mixture (i-III) containing an alkyl (meth)acrylate, a hydrophobe, and an emulsifier. 
     
     
         31 . (canceled) 
     
     
         32 . (canceled) 
     
     
         33 . A graft copolymer (B-III) comprising: the rubbery polymer (A-III) according to  claim 29 ; and at least one monomer selected from aromatic vinyl compounds, (meth)acrylic acid esters, and vinyl cyanide compounds graft-polymerized onto the rubbery polymer (A-III). 
     
     
         34 . (canceled) 
     
     
         35 . (canceled) 
     
     
         36 . A thermoplastic resin composition comprising the graft copolymer (B-III) according to  claim 33 . 
     
     
         37 . A molded article obtained by molding the thermoplastic resin composition according to  claim 36 . 
     
     
         38 . A graft crosslinked particles (B-I) according to  claim 14 ; and a thermoplastic resin (D-I). 
     
     
         39 . A graft crosslinked particles (B-II) according to  claim 24 ; and a thermoplastic resin (D-II).