Liquid crystal aligning agent containing crosslinking agent and polymer that has site having isocyanate group and/or blocked isocyanate group and site having photoreactivity, liquid crystal alignment film, and liquid crystal display element

Patent metadata

Field	Value
Publication number	US-11028323-B2
Application number	US-201616066438-A
Country	US
Kind code	B2
Filing date	Dec 27, 2016
Priority date	Dec 28, 2015
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

Provided is a liquid crystal display element that can be baked at a low temperature when forming a liquid crystal alignment film capable of imparting an alignment regulating property and a pretilt angle developing property via a photoalignment method. Further provided is a liquid crystal display element in which the liquid crystal pretilt angles are highly stable, and display burn-in hardly occurs even due to long usage. Further provided are a vertical liquid crystal alignment film to be used in the liquid crystal display element, and a liquid crystal aligning agent with which it is possible to provide the vertical liquid crystal alignment film. A liquid crystal aligning agent of the present invention contains: component (A), which is a polymer including (A-1) a site having an isocyanate group and/or a blocked isocyanate group and (A-2) a site having photoreactivity; component (B), which is a compound having, in a molecule, at least two functional groups of at least one type selected from the group consisting of an amino group and a hydroxyl group; and an organic solvent.

First claim

What is claimed is:

1. A liquid crystal aligning agent comprising the following component (A), the following component (B), and an organic solvent:
Component (A): a polymer comprising a (A-1) site having an isocyanate group and/or a blocked isocyanate group; and a (A-2) site having photoalignment;
Component (B): a compound comprising in a molecule of the compound two or more functional groups, each of which is at least one selected from the group consisting of an amino group and a hydroxyl group,
wherein the (A-1) site having an isocyanate group and/or a blocked isocyanate group is represented by following formula (1), wherein Ia represents an isocyanate group or a blocked isocyanate group,
Sa represents a spacer unit, the bonding pointer left of Sa represents bonding to the backbone of a polymer of the component (A) optionally via a spacer:
—S a —I a   (1),

wherein the (A-1) site having an isocyanate group and/or a blocked isocyanate group is derived from a monomer represented by the formula (1m),
M a -M b S a —I a ] c   (1m);

wherein Ma represents a first polymerizable group,
Mb represents a single bond, a divalent heterocycle, a trivalent heterocycle, a tetravalent heterocycle, a substituted or unsubstituted linear or branched alkyl group having a carbon number of 1 to 10, a divalent aromatic group, a trivalent aromatic group, a tetravalent aromatic ring, a divalent alicyclic group, a trivalent alicyclic group, a tetravalent alicyclic group, a divalent condensed cyclic group, a trivalent condensed cyclic group or a tetravalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group,
Sa represents a spacer unit,
Ia represents an isocyanate group or a blocked isocyanate group, and
c represents an integer of 1 to 3; and
wherein Sa in the formula (1) and/or the formula (1m) is represented by the formula (2):
—W 1 -A 1 -W 2 -A 2 -W 3 —  (2)

wherein the bonding left of W 1 represents bonding to Mb,
the bonding right of W 3 represents bonding to Ia,
W 1 , W 2 , and W 3 each independently represents a single bond, a divalent heterocycle, —(CH 2 ) n — wherein n represents 1 to 20, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF 2 O—, —OCF 2 —, —CF 2 CF 2 — or —C≡C—, wherein one or more non-adjacent CH 2 groups in these substituents may be independently substituted with —O—, —CO—, —CO—O—, —O—CO—, —Si(CH 3 ) 2 —O—Si(CH 3 ) 2 —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—O—, wherein R represents independently a hydrogen or a linear or branched alkyl group having a carbon number of 1 to 5,
A 1 and A 2 each independently represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group.

2. The liquid crystal aligning agent according to claim 1 , wherein Ia in the formula (1) is selected from the group consisting of the following structures Ia-1 to Ia-8:

wherein the broken line represents bonding to Sa in the formula (1), and
R 6 represents a linear or branched alkyl group having a carbon number of 1 to 10, wherein one or more non-adjacent CH 2 groups may be independently substituted with an oxygen atom.

3. The liquid crystal aligning agent according to claim 1 , wherein the (A-2) site having photoalignment is represented by the following formula (3):
—S b —I b   (3)

wherein Ib is a monovalent organic group comprising a photoreactive group having photoalignment,
Sb represents a spacer unit, the bonding pointer left of Sb means bonding to the backbone of the polymer of the component (A) optionally via a spacer.

4. The liquid crystal aligning agent according to claim 1 , wherein the (A-2) site having photoalignment is derived from a monomer represented by the following formula (3m):
M c -M d S b —I b ) d   (3m),

wherein Mc represents a second polymerizable group,
M d represents a single bond, a divalent heterocycle, a trivalent heterocycle, a tetravalent heterocycle, a substituted or unsubstituted linear or branched alkyl group having a carbon number of 1 to 10, a divalent aromatic group, a trivalent aromatic group, a tetravalent aromatic ring, a divalent alicyclic group, a trivalent alicyclic group, a tetravalent alicyclic group, a divalent condensed cyclic group, a trivalent condensed cyclic group or a tetravalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group,
Sb represents a spacer unit,
Ib is a monovalent organic group having a photoreactive group having photoalignment, and
d is an integer of 1 to 3.

5. The liquid crystal aligning agent according to claim 4 , wherein Sb is the formula (3m) is represented by the following formula (2):
—W 1 -A 1 -W 2 -A 2 -W 3 —  (2),

wherein bonding left of W 1 represents bonding to Md,
bonding right of W 3 represents bonding to I b ,
W 1 , W 2 , and W 3 each independently represents a single bond, a divalent heterocycle, —(CH 2 ) n — wherein n represents 1 to 20, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF 2 O—, —OCF 2 —, —CF 2 CF 2 — or —C≡C—, wherein one or more non-adjacent CH 2 groups in these substituents may be independently substituted with —O—, —CO—, —CO—O—, —O—CO—, —Si(CH 3 ) 2 —O—Si(CH 3 ) 2 —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—O— wherein R independently represents a hydrogen or a linear or branched alkyl group having a carbon number of 1 to 5,
A 1 and A 2 each independently represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.

6. The liquid crystal aligning agent according to claim 3 , wherein the photoreactive group of the formula Ib has the group represented by the following formulae (III)-1 to (III)-4:

7. The liquid crystal aligning agent according to claim 4 , wherein the monomer represented by the formula (3m) is a monomer represented by the following formula (3m)-1:

wherein Mc, Md and d are as defined in claim 4 ,
Sb is an alkylene group having a carbon number of 1 to 10 or a divalent aromatic group,
Z is an oxygen atom or a sulfur atom,
Xa and Xb each represents independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having a carbon number of 1 to 3,
R 1 is a single bond, an oxygen atom, —COO— or —OCO—,
R 2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
R 3 is a single bond, an oxygen atom, —COO— or —OCO—,
R 4 is an alkyl group having a carbon number of 1 to 20 or a monovalent organic group including an alicyclic group having an carbon number of 3 to 20,
R 5 represents a fluori

Assignees

• Nissan Chemical Ind Ltd

Inventors

• Suzuki Kanako
• Moriuchi Masato
• Ashizawa Ryoichi
• Goto Kohei

Classifications

• C08F220/303

  and one or more carboxylic moieties in the chain · CPC title

• G02F1/133742

  for homeotropic alignment · CPC title

• C08G18/8166

  with unsaturated monofunctional alcohols or amines · CPC title

• C08G18/6755

  Unsaturated carboxylic acids · CPC title

• C08G18/3284

  containing four hydroxy groups · CPC title