# US 11,028,323 B2 · 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

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- Number: US 11,028,323 B2
- Document ID: US11028323B2
- Status: Granted
- Kind: B2
- Application number: 16/066,438
- Filed: 2016-12-27
- Published: 2019-01-24
- Granted: 2021-06-08
- Earliest claimed: 2015-12-28
- Assignees: Nissan Chemical Industries, Ltd.
- Applicants: Nissan Chemical Industries, Ltd.
- Inventors: Kanako Suzuki; Masato Moriuchi; Ryoichi Ashizawa; Kohei Goto
- Web page: https://patentgrep.com/patent/US11028323B2

## CPC

- C09K 19/56: Aligning agents
- C08F 120/20: of polyhydric alcohols or {polyhydric} phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate}
- C08F 220/303: {and one or more carboxylic moieties in the chain}
- C08F 220/36: containing oxygen in addition to the carboxy oxygen {, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate}
- C08G 18/08: Processes
- C08G 18/3215: {containing aromatic groups or benzoquinone groups}
- C08G 18/3243: {containing two or more aromatic rings}
- C08G 18/3284: {containing four hydroxy groups}
- C08G 18/6755: {Unsaturated carboxylic acids}
- C08G 18/8116: {esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group}
- C08G 18/8166: {with unsaturated monofunctional alcohols or amines}
- C08G 18/8175: {with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen}
- C08L 75/04: Polyurethanes
- C08L 75/14: Polyurethanes having carbon-to-carbon unsaturated bonds
- G02F 1/133711: {by organic films, e.g. polymeric films}
- G02F 1/133742: {for homeotropic alignment}
- G02F 1/133788: {by light irradiation, e.g. linearly polarised light photo-polymerisation}
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS

## 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.

## Claims

### Claim 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:
—Sa—Ia (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),
Ma-MbSa—Ia]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):
—W1-A1-W2-A2-W3— (2)
wherein the bonding left of W1 represents bonding to Mb,
the bonding right of W3 represents bonding to Ia,
W1, W2, and W3 each independently represents a single bond, a divalent heterocycle, —(CH2)n— wherein n represents 1 to 20, —OCH2—, —CH2O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF2O—, —OCF2—, —CF2CF2— or —C≡C—, wherein one or more non-adjacent CH2 groups in these substituents may be independently substituted with —O—, —CO—, —CO—O—, —O—CO—, —Si(CH3)2—O—Si(CH3)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,
A1 and A2 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.

### Claim 2 (depends on 1)

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
R6 represents a linear or branched alkyl group having a carbon number of 1 to 10, wherein one or more non-adjacent CH2 groups may be independently substituted with an oxygen atom.

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 1)

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):
Mc-MdSb—Ib)d (3m),
wherein Mc represents a second polymerizable group,
Md 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.

### Claim 5 (depends on 4)

The liquid crystal aligning agent according to claim 4, wherein Sb is the formula (3m) is represented by the following formula (2):
—W1-A1-W2-A2-W3— (2),
wherein bonding left of W1 represents bonding to Md,
bonding right of W3 represents bonding to Ib,
W1, W2, and W3 each independently represents a single bond, a divalent heterocycle, —(CH2)n— wherein n represents 1 to 20, —OCH2—, —CH2O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF2O—, —OCF2—, —CF2CF2— or —C≡C—, wherein one or more non-adjacent CH2 groups in these substituents may be independently substituted with —O—, —CO—, —CO—O—, —O—CO—, —Si(CH3)2—O—Si(CH3)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,
A1 and A2 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.

### Claim 6 (depends on 3)

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:

### Claim 7 (depends on 4)

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,
R1 is a single bond, an oxygen atom, —COO— or —OCO—,
R2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group,
R3 is a single bond, an oxygen atom, —COO— or —OCO—,
R4 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,
R5 represents a fluorine atom or a cyano group,
a is an integer of 0 to 3, and
b is an integer of 0 to 4.

### Claim 8 (depends on 1)

The liquid crystal aligning agent according to claim 1, wherein the first polymerizable group is independently at least one group selected from the group consisting of (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, acrylamide and siloxane.

### Claim 9 (depends on 4)

The liquid crystal aligning agent according to claim 4, wherein the monomer represented by the formula (3m) is selected from the group consisting of following formulae MA-1 to MA-5:

### Claim 10 (depends on 1)

The liquid crystal aligning agent according to claim 1, wherein the component (B) is represented by the following formula (4):
(TmY (4),
wherein T represents an amino group or a hydroxyl group, Y represents an organic group with a valence of m, and m is an integer of 2 or more.

### Claim 11 (depends on 1)

The liquid crystal aligning agent according to claim 1, wherein the component (A) is a polymer, which comprises and are formed from any one compound selected from the group consisting of the following formulae MA-1 to MA-5:

### Claim 12 (depends on 1)

A liquid crystal alignment film obtained from the liquid crystal aligning agent according to claim 1.

### Claim 13 (depends on 12)

A liquid crystal display element comprising the liquid crystal alignment film according to claim 12.

### Claim 14 (depends on 4)

The liquid crystal aligning agent according to claim 4, wherein the second polymerizable group is independently at least one group selected from the group consisting of (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, acrylamide and siloxane.