Polymer composition having photoalignable group, liquid crystal alignment film formed of the polymer composition, and optical device having phase difference plate formed of the liquid crystal alignment film

Abstract

To provide a photoalignable material that can yield a photoalignable film having a high optical uniformity and no alignment defect, and is excellent in sensitivity to allow photoalignment even with exposure in a short period of time, and a liquid crystal alignment film having a high alignment stability of a liquid crystal compound from the photoalignable material. A photoalignable polymer composition containing a specific photoalignable polymer and a specific polymer that is reactive with the photoalignable polymer is manufactured, and the photoalignable film is manufactured by applying the polymer composition onto a base material or the like, drying the applied composition thereon, and irradiating the dried composition with light. Furthermore, the liquid crystal alignment film is manufactured by allowing alignment of molecules of the liquid crystal compound in the photoalignment film.

What is claimed is: 
     
         1 . A photoalignable polymer composition, containing as a first component a photoalignable polymer having at least one photoalignable group and at least one polar group selected from a hydroxyl group and a carboxyl group and having none of a group which is reactive with the polar group, and as a second component a polymer having a group that is reactive with the polar group. 
     
     
         2 . The photoalignable polymer composition according to  claim 1 , wherein the polymer of the second component further has a photoalignable group. 
     
     
         3 . The photoalignable polymer composition according to  claim 1 , wherein the photoalignable group included in the photoalignable polymer of the first component has at least one kind of structures represented by formulas (I-1) to (I-3) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formulas, R 1  represents hydrogen or an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, m represents 2, 4 or 6, and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group. 
     
     
         4 . The photoalignable polymer composition according to  claim 1 , wherein the group that is included in the polymer of the second component and reacts with at least one polar group selected from the hydroxyl group and the carboxyl group is at least one group selected from an alkoxysilane group, an isocyanate group, a [1′-methylpropylideneamino]carboxyamino group, a (3,5-dimethylpyrazolyl)carbonylamino group and an epoxy group. 
     
     
         5 . The photoalignable polymer composition according to  claim 4 , wherein the group that is included in the polymer of the second component and reacts with at least one polar group selected from the hydroxyl group and the carboxyl group is an alkoxysilane group. 
     
     
         6 . The photoalignable polymer composition according to  claim 5 , wherein the polymer of the second component includes at least one kind of constitutional unit represented by formula (II-1-1) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formulas, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 2  each independently represents hydrogen, an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons, at least one of R 2  is an alkoxy group having 1 to 4 carbons, q represents an integer from 0 to 10, and x represents a mole fraction. 
     
     
         7 . The photoalignable polymer composition according to  claim 1 , wherein the photoalignable polymer of the first component includes a constitutional unit derived from a monomer having a photoalignable group, and a constitutional unit derived from at least one kind of monomer selected from the group of acrylic acid, methacrylic acid, hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to carbons, carboxyl group-containing (meth)acrylate, carboxyl group-containing itaconate and a phenolic hydroxyl group-containing (meth)acrylate. 
     
     
         8 . The photoalignable polymer composition according to  claim 7 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formulas (I-1-1) to (I-3-1) below, and at least one kind of constitutional unit derived from hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6 carbons: 
       
         
           
           
               
               
           
         
       
       wherein, in the formulas, R 1  represents hydrogen or an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, R 7  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, Z 1  represents a single bond, —COO— or —OCO—, o represents an integer from 2 to 10, p represents an integer from 0 to 2, r represents 0 or 1, y 1 , y 2  and y 3  are a mole fraction and satisfy a relationship (0<y 1 +y 2 +y 3 <1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1. 
     
     
         9 . The photoalignable polymer composition according to  claim 7 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formulas (I-1-1) to (I-3-1) below, and a constitutional unit derived from at least one kind of monomer selected from carboxyl group-containing (meth)acrylate, carboxyl group-containing itaconate and phenolic hydroxyl group-containing (meth)acrylate: 
       
         
           
           
               
               
           
         
       
       wherein, in the formulas, R 1  represents hydrogen or an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, R 7  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, Z 1  represents a single bond, —COO— or —OCO—, o is an integer from 2 to 10, p is an integer from 0 to 2, r represents 0 or 1, y 1 , y 2  and y 3  are a mole fraction and satisfy a relationship (0<y 1 +y 2 +y 3 <1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1. 
     
     
         10 . The photoalignable polymer composition according to  claim 8 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formula (I-2-1) below, and a constitutional unit derived from hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6 carbons, and the polymer of the second component includes a constitutional unit represented by formula (II-1-1) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, R 7  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, Z 1  represents a single bond, —COO— or —OCO—, o represents an integer from 2 to 10, p represents an integer from 0 to 2, r represents 0 or 1, y is a mole fraction (satisfying a relationship: 0<y<1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 2  each independently represents hydrogen, an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons, at least one of R 2  is an alkoxy group having 1 to 4 carbons, q represents an integer from 0 to 10, and x represents a mole fraction. 
     
     
         11 . The photoalignable polymer composition according to  claim 8 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formula (I-3-1) below, and a constitutional unit derived from hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6 carbons, and the polymer of the second component includes a constitutional unit represented by formula (II-1-1) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 1  represents hydrogen or an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, Z 1  represents a single bond, —COO— or —OCO—, o represents an integer from 2 to 10, p represents an integer from 0 to 2, r represents 0 or 1, y is a mole fraction (satisfying a relationship: 0<y<1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 2  each independently represents hydrogen, an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons, at least one of R 2  is an alkoxy group having 1 to 4 carbons, q represents an integer from 0 to 10, and x represents a mole fraction. 
     
     
         12 . The photoalignable polymer composition according to  claim 9 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formula (I-1-1) below, and a constitutional unit derived from at least one kind of monomer selected from carboxyl group-containing (meth)acrylate, carboxyl group-containing itaconate and phenolic hydroxyl group-containing (meth)acrylate, and the polymer of the second component includes a constitutional unit represented by formula (II-1-1) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, R 7  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, Z 1  represents a single bond, —COO— or —OCO—, o represents an integer from 2 to 10, p represents an integer from 0 to 2, r represents 0 or 1, y is a mole fraction (satisfying a relationship: 0<y<1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 2  each independently represents hydrogen, an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons, at least one of R 2  is an alkoxy group having 1 to 4 carbons, q represents an integer from 0 to 10, and x represents a mole fraction. 
     
     
         13 . The photoalignable polymer composition according to  claim 9 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formula (I-2-1) below, and a constitutional unit derived from at least one kind of monomer selected from carboxyl group-containing (meth)acrylate, carboxyl group-containing itaconate and phenolic hydroxyl group-containing (meth)acrylate, and the polymer of the second component includes a constitutional unit represented by formula (II-1-1) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, R 7  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, Z′ represents a single bond, —COO— or —OCO—, o represents an integer from 2 to 10, p represents an integer from 0 to 2, r represents 0 or 1, y is a mole fraction (satisfying a relationship: 0<y<1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 2  each independently represents hydrogen, an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons, at least one of R 2  is an alkoxy group having 1 to 4 carbons, q represents an integer from 0 to 10, and x represents a mole fraction. 
     
     
         14 . The photoalignable polymer composition according to  claim 9 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formula (I-3-1) below, and a constitutional unit derived from at least one kind of monomer selected from carboxyl group-containing (meth)acrylate, carboxyl group-containing itaconate and phenolic hydroxyl group-containing (meth)acrylate, and the polymer of the second component includes a constitutional unit represented by formula (II-1-1) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 1  represents hydrogen or an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, Z 1  represents a single bond, —COO— or —OCO—, o represents an integer from 2 to 10, p represents an integer from 0 to 2, r represents 0 or 1, y is a mole fraction (satisfying a relationship: 0<y<1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 2  each independently represents hydrogen, an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons, at least one of R 2  is an alkoxy group having 1 to 4 carbons, q represents an integer from 0 to 10, and x represents a mole fraction. 
     
     
         15 . The photoalignable polymer composition according to  claim 8 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formulas (I-1-1) to (I-3-1) below, and a constitutional unit derived from hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6 carbons, and the polymer of the second component includes a constitutional unit represented by formula (II-2-1) or (II-3-1): 
       
         
           
           
               
               
           
         
       
       wherein, in the formulas, R 1  represents hydrogen or an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, R 7  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, Z 1  represents a single bond, —COO— or —OCO—, o is an integer from 2 to 10, p is an integer from 0 to 2, r represents 0 or 1, y 1 , y 2  and y 3  are a mole fraction and satisfy a relationship (0<y 1 +y 2 +y 3 <1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, L represents —CH 2 CH 2 — or —CH 2 CH 2 OCH 2 CH 2 —, R 4  represents a group represented by formula (II-3-1-1) or (II-3-1-2) below, and z represents a mole fraction: 
       
         
           
           
               
               
           
         
       
     
     
         16 . The photoalignable polymer composition according to  claim 9 , wherein the photoalignable polymer of the first component includes at least one kind of constitutional unit represented by formulas (I-1-1) to (I-3-1) below, and a constitutional unit derived from at least one kind of monomer selected from carboxyl group-containing (meth)acrylate, carboxyl group-containing itaconate and phenolic hydroxyl group-containing (meth)acrylate, and the polymer of the second component includes a constitutional unit represented by formula (II-4-1) below: 
       
         
           
           
               
               
           
         
       
       wherein, in the formulas, R 1  represents hydrogen or an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, R 3  represents hydrogen, an alkyl group having 1 to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, or a group represented by formula (I-4) below, R 7  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, Z 1  represents a single bond, —COO— or —OCO—, o is an integer from 2 to 10, p is an integer from 0 to 2, r represents 0 or 1, y 1 , y 2  and y 3  are a mole fraction and satisfy a relationship (0<y 1 +y 2 +y 3 <1), and arbitrary hydrogen of a phenylene group may be replaced by fluorine, a methyl group or a methoxy group: 
       
         
           
           
               
               
           
         
       
       wherein, in the formula, R 8  represents hydrogen or a methyl group, and g represents 0 or 1: 
       
         
           
           
               
               
           
         
       
       wherein, in the formulas, R 3  represents hydrogen, an alkyl group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine, T represents a methylene group having 1 to 20 carbons in which oxygen may be substituted for arbitrary carbon (however, oxygen is not substituted for adjacent carbons simultaneously), S represents a group represented by formula (II-4-1-1), (II-4-1-2) or (II-4-1-3), R 8  represents a methyl group or an ethyl group, and w represents a mole fraction. 
     
     
         17 . The photoalignable polymer composition according to  claim 1 , wherein a ratio of the first component is in the range of 50.00 to 99.99% by mass and a ratio of the second component is in the range of 0.01 to 50.00% by mass, based on the total mass of the first component and the second component. 
     
     
         18 . The photoalignable polymer composition according to  claim 1 , wherein a ratio of the first component is in the range of 70.00 to 99.50% by mass and a ratio of the second component is in the range of 0.50 to 30.00% by mass, based on the total mass of the first component and the second component. 
     
     
         19 . The photoalignable polymer composition according to any one of  claim 1 , containing at least one kind of material selected from a sensitizer and a crosslinking agent in the range of 0.01 to 50% by mass based on the total mass of the first component and the second component. 
     
     
         20 . The photoalignable polymer composition according to  claim 1 , containing at least one kind of material selected from an acid compound, a thermal acid generator and a photoacid generator in the range of 0.01 to 50% by mass based on the total mass of the first component and the second component. 
     
     
         21 . The photoalignable polymer composition according to  claim 1 , further containing a glycol solvent or a glycol ether solvent that can dissolve the first component and the second component. 
     
     
         22 . A liquid crystal alignment film formed of the photoalignable polymer composition according to  claim 1 . 
     
     
         23 . An optical device, comprising a phase difference plate prepared using the photoalignable polymer composition according to  claim 1 . 
     
     
         24 . A patterned phase difference plate prepared from the photoalignable polymer composition according to  claim 1 .