Polycarbonate diol and producing method thereof, and polyurethane and active energy ray-curable polymer composition both formed using same

Abstract

The present invention provides a novel polycarbonate diol and a polyurethane using the polycarbonate diol as raw materials. The novel polycarbonate diol produces polycarbonate diol-based polyurethane which has a high degree of hardness, superior abrasion resistance, and superior hydrophilicity, and is usable for an application such as a paint, a coating agent, a synthetic leather, an artificial leather, and a highly-functional elastomers, or the like. The present invention also provides an active-energy radiation curable polymer composition giving a cured film having a superior contamination resistance and high degree of hardness. The present invention is obtained, for example, by reacting specific two types of diols with diester carbonate in the presence of a transesterification catalyst being a compound using a metal of Group 1 or 2 on the periodic table. The present invention provides a polycarbonate diol wherein the metal content of the transesterification catalyst is 100 weight ppm or less, a polyurethane obtainable by using this polycarbonate diol and an active-energy radiation curable polymer composition containing the urethane(meth)acrylate oligomer which is obtained from the polycarbonate diol.

1 - 20 . (canceled) 
     
     
         21 . A polycarbonate diol, obtained by reacting (i) at least one of diols selected from isosorbide, isomannide and isoidide, (ii) a diol having 1 to 15 carbons which may contain hetero atom, and (iii) a diester carbonate, by use of a transesterification catalyst, wherein,
 the transesterification catalyst is either a compound using a metal of Group 1 or a compound using a metal of Group 2 on the periodic table; and   the amount of the transesterification catalyst contained in the polycarbonate diol is 100 ppm or less as the weight ratio of the metal;   the polycarbonate diol has a content of a repeating unit of the following formula (A) of 10 mass % or more:   
       
         
           
           
               
               
           
         
         the polycarbonate diol has a number average molecular weight of 500 or more and 5,000 or less; and 
         the average number of hydroxyl groups per molecule in the polycarbonate diol is 1.8 or more and 2.2 or less. 
       
     
     
         22 . The polycarbonate diol according to  claim 21 , wherein the number average molecular weight of the polycarbonate diol is 900 or less. 
     
     
         23 . The polycarbonate diol according to  claim 21 , wherein the molecular weight distribution of the polycarbonate diol is 1.5 to 2.0. 
     
     
         24 . The polycarbonate diol according to  claim 21 , wherein the amount of the transesterification catalyst contained in the polycarbonate diol is 0.1 ppm or more as the weight ratio of the metal. 
     
     
         25 . The polycarbonate diol according to  claim 21 , wherein the transesterification catalyst is a compound using a metal of Group 2 on the periodic table. 
     
     
         26 . The polycarbonate diol according to  claim 21 , wherein at least part of a molecular chain includes a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B), and
 the number average molecular weight is 250 or more and 900 or less, and   the Terminal (A) ratio represented by the following formula (I) is 1.2 or more and 1.9 or less;   
       
         
           
           
               
               
           
         
         wherein X represents a divalent group having 1 to 15 carbons which may contain hetero atom;
   Terminal ( A ) ratio ( I )={(The number of structure ( A ) in molecular chain terminal)/(The total number of structures ( A ) and ( B ) in molecular chain terminal)}/{(The number of structure ( A ) in molecular chain)/(The total number of structures ( A ) and ( B ) in molecular chain)}. 
 
       
     
     
         27 . The polycarbonate diol according to  claim 21 , wherein the diester carbonate is diphenyl carbonate. 
     
     
         28 . The polycarbonate diol according to  claim 21 , wherein the content of the diphenyl carbonate is 1 weight % or less. 
     
     
         29 . The polycarbonate diol according to  claim 21 , wherein 5% or less of molecular chain terminals are either alkyloxy group or aryloxy group among all terminals of the molecular chains. 
     
     
         30 . The polycarbonate diol according to  claim 21 , wherein the value of Hazen color number (APHA value: according to JIS K0071-1) is 100 or less. 
     
     
         31 . The polycarbonate diol according to  claim 21 , wherein 95% or more of the molecular chain terminals of the polycarbonate diol are hydroxyl groups. 
     
     
         32 . A polycarbonate diol, wherein at least part of a molecular chain includes a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B), the content of the repeating unit of the formula (A) is 10 mass % or more, the number average molecular weight is 500 or more and 5,000 or less, the average number of hydroxyl groups per molecule in the polycarbonate diol is 1.8 or more and 2.2 or less, and the terminal (A) ratio represented by the following formula (I) is 1.2 or more and 1.9 or less; 
       
         
           
           
               
               
           
         
         wherein X represents a divalent group having 1 to 15 carbons which may contain hetero atom;
   Terminal ( A ) ratio ( I )={(The number of structure ( A ) in molecular chain terminal)/(The total number of structures ( A ) and ( B ) in molecular chain terminal)}/{(The number of structure ( A ) in molecular chain)/(The total number of structures ( A ) and ( B ) in molecular chain)}. 
 
       
     
     
         33 . The polycarbonate diol according to  claim 32 , wherein the number average molecular weight is 500 or more and 900 or less. 
     
     
         34 . A polycarbonate diol producing method, comprising;
 reacting (i) at least one of diols selected from isosorbide, isomannide and isoidide, (ii) a diol having 1 to 15 carbons which may contain hetero atom, and (iii) a diester carbonate, by use of a transesterification catalyst, and   wherein the highest temperature for the reaction is lower than 180° C.;   and wherein   the polycarbonate diol has a content of a repeating unit of the following formula (A) of 10 mass % or more:   
       
         
           
           
               
               
           
         
         the polycarbonate diol has a number average molecular weight of 500 or more and 5,000 or less; and 
         the average number of hydroxyl groups per molecule in the polycarbonate diol is 1.8 or more and 2.2 or less. 
       
     
     
         35 . The polycarbonate diol obtained by the polycarbonate diol producing method according to  claim 34 .