Urethane (meth)acrylate oblgomer and sheet using the same

Abstract

Disclosed is a urethane (meth)acrylate oligomer which is obtained by reacting at least one polyoxyalkylene polyol (A), at least one monool (B1) soluble in the component (A) and/or at least one silane coupling agent (B2) reactive with an isocyanate group, at least one polyisocyanate (C) and at least one hydroxylated mono(meth)acrylate compound (D) at a ratio at which the equivalent weights of hydroxy groups, active hydrogen groups and isocyanate groups in the respective components satisfy the following formulae (1)-(3). The urethane (meth)acrylate oligomer does not substantially contain an unreacted isocyanate group. B(active hydrogen)+D(OH)=C(NCO)−A(OH) (1) 1.05≦C(NCO)/A(OH)≦2 (2) {C(NCO)−2A(OH)+2 m}×0.35≦D(OH)≦{C(NCO)−2A(OH)+2 m}×0.70 (3) In the formulae (1)-(3), A(OH) represents the total equivalent weight of hydroxy groups contained in the component (A); B(active hydrogen) represents the total equivalent weight of active hydrogen groups contained in the component (B1) and/or the component (B2); C(NCO) represents the total equivalent weight of isocyanate groups contained in the component (C); D(OH) represents the total equivalent weight of hydroxy groups contained in the component (D); and m represents the number of moles of the component (A).

1 . An urethane (meth)acrylate oligomer substantially free of unreacted isocyanate group, the urethane (meth)acrylate oligomer being obtainable by reacting at least one polyoxyalkylene polyol (A), at least one monool (B1) which is soluble in the component (A) and/or at least one silane coupling agent (B2) which can react with isocyanate group, at least one polyisocyanate (C), and at least one hydroxy group-containing mono(meth)acrylate compound (D) at a ratio so that the equivalent weights of the hydroxy group, active hydrogen group, and isocyanate group of the respective components satisfy the following formulae (1) to (3):
   B(active hydrogen)+D(OH)=C(NCO)−A(OH)  b 1)     1.05≦C(NCO)/A(OH)≦2  (2)     {C(NCO)−2A(OH)+2 m}×0.35≦D(OH){C(NCO)−2A(OH)+2 m}×0.70  (3)   wherein in the formulae (1) to (3), A(OH) represents the total equivalent weight of the hydroxy group of the component (A), B(active hydrogen) represents the total equivalent weight of the active hydrogen group of the component (B1) and/or (B2), C(NCO) represents the total equivalent weight of the total equivalent weight of the isocyanate group of the component (C), and D(OH) represents the total equivalent weight of the hydroxy group of the component (D), and m represents the number of moles of the component (A).   
     
     
         2 . The urethane (meth)acrylate oligomer according to  claim 1 , wherein the component (A) is diol and/or triol. 
     
     
         3 . The urethane (meth)acrylate oligomer according to  claim 1 , wherein at least one selected from the group consisting of the components (A), (B1), and (B2) comprises an ethylene oxide unit. 
     
     
         4 . The urethane (meth)acrylate oligomer according to  claim 1 , wherein the component (A) is polyoxyalkylene polyol having a number average molecular weight within the range of 1000 to 20000 and being obtainable by condensation of an aliphatic, alicyclic, or aromatic compound containing two or more hydroxyl groups with oxyalkylene having 2 to 4 carbon atoms. 
     
     
         5 . The urethane (meth)acrylate oligomer according to  claim 1 , wherein the component (B1) is polyoxyalkylene monool, acryl monool, castor oil-based monool, or natural or synthetic monool having 6 or more carbon atoms. 
     
     
         6 . The urethane (meth)acrylate oligomer according to  claim 1 , wherein the component (C) is an aliphatic, alicyclic, or aromatic diisocyanate containing two isocyanate groups. 
     
     
         7 . The urethane (meth)acrylate oligomer according to  claim 1 , wherein the component (D) is an ester of (meth)acrylic acid and an aliphatic, alicyclic, or aromatic diol. 
     
     
         8 . A photocurable composition comprising the urethane (meth)acrylate oligomer according to  claim 1 , and a photopolymerization initiator. 
     
     
         9 . The photocurable composition according to  claim 8 , which further comprises a hydroxy group-containing (meth)acrylate compound. 
     
     
         10 . The photocurable composition according to  claim 8 , which further comprises acryl syrup. 
     
     
         11 . A sheet obtainable by forming a photocurable composition layer from the photocurable composition according to  claim 8 , and then curing the layer with photoirradiation. 
     
     
         12 . A method for producing an urethane (meth)acrylate oligomer, comprising the step of reacting at least one polyoxyalkylene polyol (A), at least one monool (B1) which is soluble in the component (A) and/or at least one silane coupling agent (B2) which can react with isocyanate group, at least one polyisocyanate (C), and at least one hydroxy group-containing mono(meth)acrylate compound (D) at a ratio so that the equivalent weights of the hydroxy group, active hydrogen group, and isocyanate group of the respective components satisfy the following formulae (1) to (3):
   B(active hydrogen)+D(OH)=C(NCO)−A(OH)  (1)     1.05≦C(NCO)/A(OH)≦2  (2)     {C(NCO)−2A(OH)+2 m}×0.35≦D(OH){C(NCO)−2A(OH)+2 m}×0.70  (3)   wherein in the formulae (1) to (3), A(OH) represents the total equivalent weight of the hydroxy group of the component (A), B(active hydrogen) represents the total equivalent weight of the active hydrogen group of the component (B1) and/or (B2), C(NCO) represents the total equivalent weight of the total equivalent weight of the isocyanate group of the component (C), and D(OH) represents the total equivalent weight of the hydroxy group of the component (D), and m represents the number of moles of the component (A),   
       and so that the urethane (meth)acrylate oligomer is substantially free of unreacted isocyanate group. 
     
     
         13 . The urethane (meth)acrylate oligomer according to  claim 2 , wherein at least one selected from the group consisting of the components (A), (B1), and (B2) comprises an ethylene oxide unit. 
     
     
         14 . The urethane (meth)acrylate oligomer according to  claim 2 , wherein the component (A) is polyoxyalkylene polyol having a number average molecular weight within the range of 1000 to 20000 and being obtainable by condensation of an aliphatic, alicyclic, or aromatic compound containing two or more hydroxyl groups with oxyalkylene having 2 to 4 carbon atoms. 
     
     
         15 . The urethane (meth)acrylate oligomer according to  claim 2 , wherein the component (B1) is polyoxyalkylene monool, acryl monool, castor oil-based monool, or natural or synthetic monool having 6 or more carbon atoms. 
     
     
         16 . The urethane (meth)acrylate oligomer according to  claim 2 , wherein the component (C) is an aliphatic, alicyclic, or aromatic diisocyanate containing two isocyanate groups. 
     
     
         17 . The urethane (meth)acrylate oligomer according to  claim 2 , wherein the component (D) is an ester of (meth)acrylic acid and an aliphatic, alicyclic, or aromatic diol. 
     
     
         18 . A sheet obtainable by forming a photocurable composition layer from the photocurable composition according to  claim 9 , and then curing the layer with photoirradiation. 
     
     
         19 . A sheet obtainable by forming a photocurable composition layer from the photocurable composition according to  claim 10 , and then curing the layer with photoirradiation.