Epoxidized block copolymer, its production, and its composition

Abstract

The present invention is directed to an epoxidized block copolymer (E) obtained by epoxidizing a block copolymer (C) comprising a polymer block (A) composed mainly of a vinyl aromatic hydrocarbon compound and a polymer block (B) composed mainly of a conjugated diene compound or a product (D) of hydrogenation of the block copolymer (C). The epoxidized block copolymer (E) meets at least one of the following requisites: (1) having a molar ratio (R) of contained hydroxyl to epoxy ranging from 0.001 to 0.1, the molar ratio (R) being represented by the formula: R=[hydroxyl]/[epoxy] (wherein [hydroxyl] represents the amount, in terms of the number of moles, of hydroxyl contained per unit weight of the epoxidized block copolymer and [epoxy] represents the amount, in terms of the number of moles, of epoxy contained per unit weight of the epoxidized block copolymer); (2) having a gel content of not greater than 5% by weight; and (3) having a chloride ion content of not greater than 7 ppm. This epoxidized block copolymer can be obtained by epoxidizing the above block copolymer in an organic solvent and evaporating off the organic solvent, and compositions comprising the same together with other compounds and resins are useful.

What is claimed is:  
     
         1 . An epoxidized block copolymer (E) obtained by epoxidizing a block copolymer (C) comprising a polymer block (A) composed mainly of a vinyl aromatic hydrocarbon compound and a polymer block (B) composed mainly of a conjugated diene compound or a hydrogenation product (D) of the block copolymer (C), said epoxidized block copolymer (E) meeting at least one of Requisites (1)-(3): 
 (1) having a molar ratio (R) of contained hydroxyl to epoxy ranging from 0.001 to 0.1, said molar ratio (R) being represented by the formula:    R=[hydroxyl]/[epoxy]   wherein [hydroxyl] represents the amount, in terms of the number of moles, of hydroxyl contained per unit weight of the epoxidized block copolymer and [epoxy] represents the amount, in terms of the number of moles, of epoxy contained per unit weight of the epoxidized block copolymer;    (2) having a gel content of not greater than 5% by weight; and    (3) having a chloride ion content of not greater than 7 ppm.    
     
     
         2 . The epoxidized block copolymer (E) according to  claim 1 , which further meets at least one of Requisites (4) to (6): 
 (4) having an acid value of not greater than 10 mgKOH/g;    (5) having a residual organic solvent content of not greater than 5000 ppm; and    (6) having an epoxy equivalent of 140 to 2700.    
     
     
         3 . The epoxidized block copolymer (E) according to  claim 2 , which meets Requisites (1) to (6).  
     
     
         4 . A thermoplastic resin composition comprising (i) a thermoplastic resin and (ii) an epoxidized block copolymer (E) obtained by epoxidizing a block copolymer (C) comprising a polymer block (A) composed mainly of a vinyl aromatic hydrocarbon compound and a polymer block (B) composed mainly of a conjugated diene compound or a hydrogenation product (D) of the block copolymer (C), said epoxidized block copolymer (E) meeting Requisites (1) and (2): 
 (1) having a molar ratio (R) of contained hydroxyl to epoxy ranging from 0.001 to 0.1, said molar ratio (R) being represented by the formula:    R=[hydroxyl]/[epoxy]   wherein [hydroxyl] represents the amount, in terms of the number of moles, of hydroxyl contained per unit weight of the epoxidized block copolymer and [epoxy] represents the amount, in terms of the number of moles, of epoxy contained per unit weight of the epoxidized block copolymer;    (2) having a gel content of not greater than 5% by weight.    
     
     
         5 . The composition as claimed in  claim 4 , in which said epoxidized block copolymer (E) further meets Requisites (4), (5) and (6): 
 (4) having an acid value of not greater than 10 mgKOH/g;    (5) having a residual organic solvent content of not greater than 5000 ppm; and    (6) having an epoxy equivalent of 140 to 2700.    
     
     
         6 . The composition as claimed in  claim 4 , in which the molar ratio (R) ranges from 0.001 to 0.05.  
     
     
         7 . The composition as claimed in  claim 5 , in which the acid value is not greater than 5 mgKOH/g.  
     
     
         8 . The composition as claimed in  claim 4 , in which the gel content is 0.0001 to 1 % by weight.  
     
     
         9 . The composition as claimed in  claim 4 , in which the thermoplastic resin is at least one selected from the group consisting of a polyester, a polycarbonate, a styrene copolymer, a polyolefin, a polyurethane, a polyamide and a thermoplastic elastomer.  
     
     
         10 . The composition as claimed in  claim 4 , in which the weight ratio of (i) to (ii) is 1/99 to 99/1.  
     
     
         11 . The composition as claimed in  claim 4 , in which the weight ratio of (i) to (ii) is 60/40 to 95/5.  
     
     
         12 . A anti-blocking, transparent composition comprising 0.001 to 5 parts by weight of (i′) at least one compound selected from the group consisting of a silicon compound, a fatty acid salt, a fatty acid ester, a fatty acid amide and a nonionic surfactant and 100 parts by weight of (ii) an epoxidized block copolymer (E) obtained by epoxidizing a block copolymer (C) comprising a polymer block (A) composed mainly of a vinyl aromatic hydrocarbon compound and a polymer block (B) composed mainly of a conjugated diene compound or a hydrogenation product (D) of the block copolymer (C), said epoxidized block copolymer (E) meeting Requisites (1) and (2): 
 (1) having a molar ratio (R) of contained hydroxyl to epoxy ranging from 0.001 to 0.1, said molar ratio (R) being represented by the formula:  
 R=[hydroxyl]/[epoxy] 
 wherein [hydroxyl] represents the amount, in terms of the number of moles, of hydroxyl contained per unit weight of the epoxidized block copolymer and [epoxy] represents the amount, in terms of the number of moles, of epoxy contained per unit weight of the epoxidized block copolymer;  
 (2) having a gel content of not greater than 5% by weight.  
 
     
     
         13 . The composition as claimed in  claim 12 , in which said epoxidized block copolymer (E) further meets Requisites (4), (5) and (6): 
 (4) having an acid value of not greater than 10 mgKOH/g;    (5) having a residual organic solvent content of not greater than 5000 ppm; and    (6) having an epoxy equivalent of 140 to 2700.    
     
     
         14 . The composition as claimed in  claim 12 , in which the molar ratio (R) ranges from 0.001 to 0.05.  
     
     
         15 . The composition as claimed in  claim 13 , in which the acid value is not greater than 5 mgKOH/g.  
     
     
         16 . The composition as claimed in  claim 13 , in which the gel content is 0.0001 to 1 % by weight.  
     
     
         17 . A heat-stabilized composition comprising 0.001 to 5 parts by weight of at least one compound selected from the group consisting of tetrakis(methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate) methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4′-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-methylphenol, trisnonylphenyl phosphite and tris(2,5-di-tert-butylphenyl) phosphite and 100 parts by weight of (ii) an epoxidized block copolymer (E) obtained by epoxidizing a block copolymer (C) comprising a polymer block (A) composed mainly of a vinyl aromatic hydrocarbon compound and a polymer block (B) composed mainly of a conjugated diene compound or a hydrogenation product (D) of the block copolymer (C), said epoxidized block copolymer (E) meeting Requisites (1) and (2): 
 (1) having a molar ratio (R) of contained hydroxyl to epoxy ranging from 0.001 to 0.1, said molar ratio (R) being represented by the formula:  
 R=[hydroxyl]/[epoxy] 
 wherein [hydroxyl] represents the amount, in terms of the number of moles, of hydroxyl contained per unit weight of the epoxidized block copolymer and [epoxy] represents the amount, in terms of the number of moles, of epoxy contained per unit weight of the epoxidized block copolymer;  
 (2) having a gel content of not greater than 5% by weight.  
 
     
     
         18 . The composition as claimed in  claim 17 , in which said epoxidized block copolymer (E) further meets Requisites (4), (5) and (6): 
 (4) having an acid value of not greater than 10 mgKOH/g;    (5) having a residual organic solvent content of not greater than 5000 ppm; and    (6) having an epoxy equivalent of 140 to 2700.    
     
     
         19 . The composition as claimed in  claim 17 , in which the molar ratio (R) ranges from 0.001 to 0.05.  
     
     
         20 . The composition as claimed in  claim 18 , in which the acid value is not greater than 5 mgKOH/g.  
     
     
         21 . The composition as claimed in  claim 18 , in which the gel content is 0.0001 to 1 % by weight.  
     
     
         22 . An adhesive film comprising an epoxidized block copolymer (E) obtained by epoxidizing a block copolymer (C) comprising a polymer block (A) composed mainly of a vinyl aromatic hydrocarbon compound and a polymer block (B) composed mainly of a conjugated diene compound or a hydrogenation product (D) of the block copolymer (C), said epoxidized block copolymer (E) meeting Requisites (1), (2), (4) and (6): 
 (1) having a molar ratio (R) of contained hydroxyl to epoxy ranging from 0.001 to 0.1, said molar ratio (R) being represented by the formula:    R=[hydroxyl]/[epoxy]   wherein [hydroxyl] represents the amount, in terms of the number of moles, of hydroxyl contained per unit weight of the epoxidized block copolymer and [epoxy] represents the amount, in terms of the number of moles, of epoxy contained per unit weight of the epoxidized block copolymer;    (2) having a gel content of not greater than 1% by weight.    (4) having an acid value of not greater than 5 mgKOH/g;    (6) having an epoxy equivalent of 140 to 2700.    
     
     
         23 . The adhesive film as claimed in  claim 22 , which further comprises a polyolefin.  
     
     
         24 . The adhesive film as claimed in  claim 23 , in which the polyolefin is a copolymer of ethylene and vinyl acetate.  
     
     
         25 . A stabilized coating composition comprising (i′″) a liquid epoxy compound and (ii) an epoxidized block copolymer (E) obtained by epoxidizing a block copolymer (C) comprising a polymer block (A) composed mainly of a vinyl aromatic hydrocarbon compound and a polymer block (P) composed mainly of a conjugated diene compound or a hydrogenation product (D) of the block copolymer (C), said epoxidized block copolymer (E) meeting Requisites (1), (2), (4) and (6): 
 (1) having a molar ratio (R) of contained hydroxyl to epoxy ranging from 0.001 to 0.1, said molar ratio (R) being represented by the formula:  
 R=[hydroxyl]/[epoxy] 
 wherein [hydroxyl] represents the amount, in terms of the number of moles, of hydroxyl contained per unit weight of the epoxidized block copolymer and [epoxy] represents the amount, in terms of the number of moles, of epoxy contained per unit weight of the epoxidized block copolymer;  
 (2) having a gel content of not greater than 1% by weight.  
 (4) having an acid value of not greater than 5 mgKOH/g;  
 (6) having an epoxy equivalent of 140 to 2700.  
 
     
     
         26 . The composition as claimed in  claim 25 , in which the liquid epoxy compound is an alicyclic compound or a bisphenyl compound.  
     
     
         27 . The composition as claimed in  claim 25 , in which the weight ratio of (i′) to (ii) ranges from 95/5 to 80/20.