Curable resin composition

Abstract

A curable resin composition includes (A) a specific curable resin and (C) a curing agent, and further includes (BI) 0.1 parts by mass or more and 20 parts by mass or less of a polyhydric alcohol having 2 to 5 hydroxyl groups, based on based on 100 parts by mass of the curable resin (A); (BII) a cyclic compound having 3 to 6 reactive groups and a reactive group equivalent of 100 g/eq or more and 300 g/eq or less; or (BIII) a specific oxetane compound in a mass ratio of the curable resin (A) to the oxetane compound (BIII) being 5:5 to 9:1.

What is claimed is: 
     
         1 . A curable resin composition comprising:
 (A) a curable resin represented by the following General Formula (1):
   Y 1 -L 3 -X 1 L 1 -X 3 -L 2 -X 2  n L 4 -Y 2   General Formula (1)
 
   where   X 1  and X 2  are independently of each other a divalent linking group containing an aromatic ring,   X 3  is an alkylene group having 4 to 18 carbon atoms, in which a carbon atom forming the alkylene group may be substituted by an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom,   L 1 , L 2 , L 3 , and L 4  are independently of one another a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ester bond, a urethane bond, an ether bond, a thiourethane bond, and a thioether bond,   Y 1  and Y 2  are independently of each other an epoxy group, a cycloalkene oxide group, or an oxetanyl group, and   n is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less; and   (C) a curing agent,   wherein the curable resin composition further comprises:   (BI) 0.1 parts by mass or more and 20 parts by mass or less of a polyhydric alcohol having 2 to 5 hydroxyl groups, based on 100 parts by mass of the curable resin (A);   (BII) a cyclic compound having 3 to 6 reactive groups and a reactive group equivalent of 100 g/eq or more and 300 g/eq or less; or   (BIII) an oxetane compound represented by the following General Formula (2):   
       
         
           
           
               
               
           
         
         where 
         X 4  is a divalent linking group which is linked by a carbon atom forming an aromatic ring, 
         X 5  and X 6  are independently of each other a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 
         L 5  and L 6  are independently of each other a divalent linking group containing a bond selected from the group consisting of —O—, —C—O—, an ester bond, and an ether bond, and 
         s is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less, 
         a mass ratio of the curable resin (A) to the oxetane compound (BIII) being 5:5 to 9:1. 
       
     
     
         2 . The curable resin composition according to  claim 1 , wherein X 1  and X 2  are a phenylene group, a biphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a fluorenediyl group, a diphenylmethanediyl group, a diphenylethanediyl group, a diphenylpropanediyl group, a diphenyletherdiyl group, or a diphenylsulfonediyl group, which is optionally substituted. 
     
     
         3 . The curable resin composition according to  claim 1 , wherein X 3  is an optionally substituted acyclic alkylene group having a straight chain or a branched chain structure. 
     
     
         4 . The curable resin composition according to  claim 1 , wherein L 1 , L 2 , L 3 , and L 4  contain a bond selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ether bond, and a thioether bond. 
     
     
         5 . The curable resin composition according to  claim 1 , wherein Y 1  and Y 2  are an epoxy group. 
     
     
         6 . The curable resin composition according to  claim 1 , wherein the curing agent (C) is a photoacid generator. 
     
     
         7 . The curable resin composition according to  claim 1 , wherein the curable resin composition comprises the polyhydric alcohol (BI), and the polyhydric alcohol (BI) has a molecular weight of 1,000 or less. 
     
     
         8 . The curable resin composition according to  claim 7 , wherein the curable resin composition further comprises an oxetane compound (D), and comprises 0.1 parts by mass or more and 20 parts by mass or less of the polyhydric alcohol (BI), based on total 100 parts by mass of the curable resin (A) and the oxetane compound (D). 
     
     
         9 . The curable resin composition according to  claim 8 , wherein the oxetane compound (D) is represented by the following General Formula (4): 
       
         
           
           
               
               
           
         
         where X 8  is a dihydric alcohol residue, or a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, an ether bond, a carbonate bond, a urethane bond, and a urea bond, and may contain an aromatic ring. 
       
     
     
         10 . The curable resin composition according to  claim 8 , wherein the curable resin composition comprises 5 parts by mass or more and 90 parts by mass or less of the oxetane compound (D), based on total 100 parts by mass of the curable resin (A) and the oxetane compound (D). 
     
     
         11 . A cured product formed by curing a curable resin composition, the curable resin composition comprising:
 (A) a curable resin represented by the following General Formula (1):
   Y 1 -L 3 -X 1 L 1 -X 3 -L 2 -X 2  n L 4 -Y 2   General Formula (1)
 
   where   X 1  and X 2  are independently of each other a divalent linking group containing an aromatic ring,   X 3  is an alkylene group having 4 to 18 carbon atoms, in which a carbon atom forming the alkylene group may be substituted by an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom,   L 1 , L 2 , L 3 , and L 4  are independently of one another a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ester bond, a urethane bond, an ether bond, a thiourethane bond, and a thioether bond,   Y 1  and Y 2  are independently of each other an epoxy group, a cycloalkene oxide group, or an oxetanyl group, and   n is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less;   (C) a curing agent; and   (BI) 0.1 parts by mass or more and 20 parts by mass or less of a polyhydric alcohol having 2 to 5 hydroxyl groups, based on 100 parts by mass of the curable resin (A), the polyhydric alcohol having a molecular weight of 1,000 or less, wherein the curable resin composition includes:   (A) a curable resin represented by the following General Formula (1):
   Y 1 -L 3 -X 1 L 1 -X 3 -L 2 -X 2  n L 4 -Y 2   General Formula (1)
 
   where   X 1  and X 2  are independently of each other a divalent linking group containing an aromatic ring,   X 3  is an alkylene group having 4 to 18 carbon atoms, in which a carbon atom forming the alkylene group may be substituted by an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom,   L 1 , L 2 , L 3 , and L 4  are independently of one another a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ester bond, a urethane bond, an ether bond, a thiourethane bond, and a thioether bond,   Y 1  and Y 2  are independently of each other an epoxy group, a cycloalkene oxide group, or an oxetanyl group, and   n is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less; and   (C) a curing agent,   and further includes:   (BI) 0.1 parts by mass or more and 20 parts by mass or less of a polyhydric alcohol having 2 to 5 hydroxyl groups, based on 100 parts by mass of the curable resin (A),   the polyhydric alcohol (BI) having a molecular weight of 1,000 or less.   
     
     
         12 . A method of manufacturing a three-dimensional shaped article, comprising:
 photocuring a curable resin composition by layer based on a slice data to shape a shaped article,
 wherein the curable resin composition includes: 
 (A) a curable resin represented by the following General Formula (1):
   Y 1 -L 3 -X 1 L 1 -X 3 -L 2 -X 2  n L 4 -Y 2   General Formula (1)
 
 
 where 
 X 1  and X 2  are independently of each other a divalent linking group containing an aromatic ring, 
 X 3  is an alkylene group having 4 to 18 carbon atoms, in which a carbon atom forming the alkylene group may be substituted by an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom, 
 L 1 , L 2 , L 3 , and L 4  are independently of one another a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ester bond, a urethane bond, an ether bond, a thiourethane bond, and a thioether bond, 
 Y 1  and Y 2  are independently of each other an epoxy group, a cycloalkene oxide group, or an oxetanyl group, and 
 n is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less; and 
 (C) a curing agent, 
 and further includes: 
 (BI) 0.1 parts by mass or more and 20 parts by mass or less of a polyhydric alcohol having 2 to 5 hydroxyl groups, based on 100 parts by mass of the curable resin (A), 
 where the polyhydric alcohol (BI) having a molecular weight of 1,000 or less. 
   
     
     
         13 . The method of manufacturing a three-dimensional shaped article according to  claim 12 , further comprising subjecting the shaped article to heat treatment to obtain the three-dimensional shaped article. 
     
     
         14 . The curable resin composition according to  claim 1 , wherein the curable resin composition comprises the cyclic compound (BII), and the cyclic compound (BII) is a compound having 1 to 6 cyclic structures selected from the group consisting of isocyanurate rings and aromatic rings. 
     
     
         15 . The curable resin composition according to  claim 14 , wherein a reactive group of the cyclic compound (BII) is an epoxy group. 
     
     
         16 . The curable resin composition according to  claim 14 , wherein the curable resin composition comprises 50 parts by mass or more and 97 parts by mass or less of the curable resin (A) and 3 parts by mass or more and 50 parts by mass or less of the cyclic compound (BII), based on total 100 parts by mass of the curable resin (A) and the cyclic compound (BII). 
     
     
         17 . The curable resin composition according to  claim 14 , wherein the curable resin composition comprises an oxetane compound (D). 
     
     
         18 . The curable resin composition according to  claim 14 , wherein the curable resin composition comprises 0 parts by mass or more and 90 parts by mass or less of the oxetane compound (D), based on total 100 parts by mass of the curable resin (A), the cyclic compound (BII), and the oxetane compound (D). 
     
     
         19 . A method of manufacturing a three-dimensional shaped article, comprising:
 photocuring a curable resin composition by layer based on a slice data to shape a shaped article,
 wherein the curable resin composition includes: 
 (A) a curable resin represented by the following General Formula (1):
   Y 1 -L 3 -X 1 L 1 -X 3 -L 2 -X 2  n L 4 -Y 2   General Formula (1)
 
 
 where 
 X 1  and X 2  are independently of each other a divalent linking group containing an aromatic ring, 
 X 3  is an alkylene group having 4 to 18 carbon atoms, in which a carbon atom forming the alkylene group may be substituted by an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom, 
 L 1 , L 2 , L 3 , and L 4  are independently of one another a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ester bond, a urethane bond, an ether bond, a thiourethane bond, and a thioether bond, 
 Y 1  and Y 2  are independently of each other an epoxy group, a cycloalkene oxide group, or an oxetanyl group, and 
 n is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less; and 
 (C) a curing agent, 
 and further includes: 
 (BII) a cyclic compound having 3 to 6 reactive groups and a reactive group equivalent of 100 g/eq or more and 300 g/eq or less, 
 the cyclic compound (BII) being a compound having 1 to 6 cyclic structures selected from the group consisting of isocyanurate rings and aromatic rings. 
   
     
     
         20 . The curable resin composition according to  claim 1 , wherein the curable resin composition comprises the oxetane compound (BIII), and the oxetane compound (BIII) is a compound having two oxetanyl groups. 
     
     
         21 . The curable resin composition according to  claim 20 , wherein a mass ratio of the curable resin (A) to the oxetane compound (BIII) is 7:3 to 9:1. 
     
     
         22 . The curable resin composition according to  claim 20 , wherein X 4  is a phenylene group, a biphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, a fluorenediyl group, a diphenylmethanediyl group, a diphenylethanediyl group, a diphenylpropanediyl group, a diphenyletherdiyl group, a diphenylsulfonediyl group, a triphenylethanediyl group, or a tetraphenylmethanediyl group, which is optionally substituted. 
     
     
         23 . A method of manufacturing a three-dimensional shaped article, comprising:
 photocuring a curable resin composition by layer based on a slice data to shape a shaped article,
 wherein the curable resin composition includes: 
 (A) a curable resin represented by the following General Formula (1):
   Y 1 -L 3 -X 1 L 1 -X 3 -L 2 -X 2  n L 4 -Y 2   General Formula (1)
 
 
 where 
 X 1  and X 2  are independently of each other a divalent linking group containing an aromatic ring, 
 X 3  is an alkylene group having 4 to 18 carbon atoms, in which a carbon atom forming the alkylene group may be substituted by an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom, 
 L 1 , L 2 , L 3 , and L 4  are independently of one another a divalent linking group containing one or more bonds selected from the group consisting of —O—, —C—O—, —S—, —C—S—, an ester bond, a urethane bond, an ether bond, a thiourethane bond, and a thioether bond, 
 Y 1  and Y 2  are independently of each other an epoxy group, a cycloalkene oxide group, or an oxetanyl group, and 
 n is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less; and 
 (C) a curing agent, 
 and further includes: 
 (BIII) an oxetane compound represented by the following General Formula (2): 
   
       
         
           
           
               
               
           
         
         
           where 
           X 4  is a divalent linking group which is linked by a carbon atom forming an aromatic ring, 
           X 5  and X 6  are independently of each other a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 
           L 5  and L 6  are independently of each other a divalent linking group containing a bond selected from the group consisting of —O—, —C—O—, an ester bond, and an ether bond, and 
           s is an average value of repeating structural units, and a real number of 0.1 or more and 10 or less, 
           a mass ratio of the curable resin (A) to the oxetane compound (BIII) being 5:5 to 9:1, 
           the oxetane compound (BIII) being a compound having two oxetanyl groups. 
         
       
     
     
         24 . The method of manufacturing a three-dimensional shaped article according to  claim 23 , further comprising subjecting the shaped article to thermal irradiation to obtain the three-dimensional shaped article.