# US 7,407,691 B2 · Photopolymerizable oxetane derivative and liquid-crystal composition containing it

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- Number: US 7,407,691 B2
- Document ID: US7407691B2
- Status: Granted
- Kind: B2
- Application number: 11/085,903
- Filed: 2005-03-21
- Published: 2005-10-13
- Granted: 2008-08-05
- Earliest claimed: 2004-04-07
- Assignees: Chisso Corporation; Chisso Petrochemical Corporation
- Inventors: Ryushi Shundo; Tomohiro Etou; Masami Kimura
- Web page: https://patentgrep.com/patent/US7407691B2

## CPC

- C07D 305/06: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
- C09K 2019/3416: {the heterocyclic ring being a four-membered ring, e.g. oxetane}
- C09K 2323/00: Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

Provided are a liquid-crystal compound and a liquid-crystal composition containing the compound, of which the advantages are that they show nematic hybrid orientation on a rubbed TAC substrate, they are polymerizable in open air and they readily give a polymer having a high degree of polymerization even when exposed to a relatively small total quantity of light. The films formed by photopolymerizing them keep nematic hybrid orientation. The compound is represented by formula (1): wherein R1 is a hydrogen or an alkyl; R2 is a hydrogen, —OCF3, etc.; A1 is a 1,4-phenylene, etc.; A2 and A3 are independently a 1,4-cyclohexylene, a 1,4-phenylene, etc.; X1 is a single bond, —O—, etc.; X2 and X3 are independently a single bond, —COO—, —C≡C—, —CONH—, etc.; m is an integer of from 0 to 20; and n is 1 or 0.

## Claims

### Claim 1

A compound of a formula (1):
wherein R1 represents a hydrogen atom or an alkyl group having from 1 to 5 carbon atoms; R2 represents a hydrogen atom, —NCO, —NCS, —OCHF2, —CH2F, —OCF2CF2H, —OCF2CHFCF3, or —Y1—(CF2)s-CF3, in which Y1 represents —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or —C≡C—, s indicates an integer of from 0 to 10; A1 represents a 1,4-phenylene group, or a 1,4-phenylene group in which any hydrogen atom is substituted with a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, a hydroxy group, a formyl group, an acetoxy group, an acetyl group, a carbonylmethyl group, a carbonyltrifluoromethyl group, a difluoromethyl group, or a trifluoromethyl group; A2 and A3 each independently represent a 1,4-cyclohexylene group, a 1,4-phenylene group, a pyridine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group, a 1,4-cyclohexylene group in which any hydrogen atom is substituted with a fluorine atom, or a 1,4-phenylene group in which any hydrogen atom is substituted with a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, a hydroxy group, a formyl group, an acetoxy group, an acetyl group, a carbonylmethyl group, a carbonyltrifluoromethyl group, a difluoromethyl group or a trifluoromethyl group; X1 represents a single bond, —O— or —OCO—; X2 and X3 each independently represent a single bond, —CH═CH—COO—, —OOC—CH═CH—, —CH2CH2—COO—, —OOC—CH2CH2—, —COO—, —OCO—, —OCH2—, —CH2O—, —OCF2—, —CF2O—, —CH2CH2—, —C≡C—, —NHCO—, or —CONH—; m indicates an integer of from 0 to 20; and n indicates 1 or 0.

### Claim 2 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —Y1—(CF2)s—CF3, in which Y1 is —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or —C≡C—, s is an integer of from 0 to 10.

### Claim 3 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —Y1—(CF2)s—CF3, in which Y1 is —O—, s is an integer of from 0 to 10; A1 is a 1,4-phenylene group, or a 1,4-phenylene group in which any hydrogen atom is substituted with a halogen atom, a methyl group, an acetyl group or a trifluoromethyl group; A2 and A3 are independently a 1,4-cyclohexylene group, a 1,4-phenylene group, a pyridine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group, or a 1,4-phenylene group in which any hydrogen atom is substituted with a halogen atom, a methyl group, an acetyl group or a trifluoromethyl group; X1 is a single bond or —O—; X2 and X3 are independently a single bond, —CH═CH—COO—, —CH2CH2—COO—, —COO—, —C≡C—, or —CONH—.

### Claim 4 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —OCF3; A1 is a 1,4-phenylene group, or a 1,4-phenylene group in which any hydrogen atom is substituted with a halogen atom, a methyl group, an acetyl group or a trifluoromethyl group; A2 and A3 are independently a 1,4-cyclohexylene group, a 1,4-phenylene group, a pyridine-2,5-diyl group, a pyridazine-3,6-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group, or a 1,4-phenylene group in which any hydrogen atom is substituted with a halogen atom, a methyl group, an acetyl group or a trifluoromethyl group; X1 is a single bond or —O—; X2 and X3 are independently a single bond, —CH═CH—COO—, —CH2CH2—COO—, —COO—, —C≡C—, or —CONH—.

### Claim 5 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —OCF3; A1 is a 1,4-phenylene group; A2 and A3 are independently a 1,4-phenylene group or a 3-fluoro-1,4-phenylene group; X1 is a single bond or —O—; X2 and X3 are independently a single bond, —CH═CH—COO—, —CH2CH2—COO—, —COO—,—C≡C—, or —CONH—; m is an integer of from 0 to 8.

### Claim 6 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —OCF3; A1 is a 1,4-phenylene group; A2 and A3 are independently a 1,4-phenylene group or a 3-fluoro-1,4-phenylene group; X1 is a single bond or —O—; X2 and X3 are independently a single bond, —CH═CH—COO—, —CH2CH2—COO—, —COO—, or —CONH—; m is an integer of from 0 to 6.

### Claim 7 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —OCF3; A1 is a 1,4-phenylene group A2 a 1,4-phenylene group or a 3-fluoro-1,4-phenylene group; X1 is a single bond or —O—; X2 is —CH═CH—COO—, —CH2CH2—COO—, —COO—, or —CONH—; m is an integer of from 0 to 6; and n is 0.

### Claim 8 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —OCF3; A1 is a 1,4-phenylene group; A2 is a 1,4-phenylene group or a 3-fluoro-1,4-phenylene group; X1 is a single bond or —O—; X2 is —COO—; m is an integer of from 0 to 6; and n is 0.

### Claim 9 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —OCF3; A1 is a 1,4-phenylene group; A2 a 1,4-phenylene group or a 3-fluoro-1,4-phenylene group; A3 is a 1,4-phenylene group; X1 is a single bond or —O—; X2 is —CH═CH—COO—, —CH2CH2—COO—, —COO—, or —CONH—; X3 is a single bond; m is an integer of from 0 to 6; and n is 1.

### Claim 10 (depends on 1)

The compound as claimed in claim 1, wherein, in formula (1), R1 is a methyl or ethyl group; R2 is —OCF3; A1, A2 and A3 is a 1,4-phenylene group; X1 is a single bond or —O—; X2 is —COO—; X3 is a single bond; m is an integer of from 0 to 6; and n is 1.

### Claim 11 (depends on 1)

A liquid-crystal composition containing at least two compounds, in which at least one compound is the compound of claim 1.

### Claim 12 (depends on 11)

The liquid-crystal composition as claimed in claim 11, wherein all the compounds are polymerizable compounds.

### Claim 13 (depends on 1, 11)

The liquid-crystal composition as claimed in claim 11, wherein at least one compound is the compound of formula (1) and at least one other compound is a polymerizable compound that differs from the compound of claim 1.

### Claim 14 (depends on 11)

The liquid-crystal composition as claimed in claim 11, wherein all the compounds are the compounds of formula (1).

### Claim 15 (depends on 11)

The liquid-crystal composition as claimed in claim 11, which contains at least one compound of formula (1) and at least one polymerizable compound selected from a group of compounds of formulae (M1), (M2), (M3), (M4) and (M5):
wherein R5 independently represents a hydrogen atom, a fluorine atom, a chlorine atom, —CN, or an alkyl group having from 1 to 20 carbon atoms; in the alkyl group, any —CH2— may be substituted with —O—, —S—, —COO—, —OCO—or —CO—, and any hydrogen may be substituted with a halogen atom; R6 independently represents a hydrogen atom or an alkyl group having from 1 to 5 carbon atoms; A4, A5, A6 and A7 each independently represent a 1,4-cyclohexylene group, a 1,4-phenylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, a fluorene-2,7-diyl group, or a 1,4-phenylene group in which any hydrogen atom is substituted with a halogen atom or a cyano group; B1 independently represents a single bond, a 1,4-phenylene group, a naphthalene-2,6-diyl group, a biphenyl-4,4′-diyl group, a fluorene-2,7-diyl group, a 9-methylfluoren-2,7-diyl group, a 9-ethylfluorene-2,7-diyl group, a 9,9-dimethylfluoren-2,7-diyl group, a 9-chlorofluorene-2,7-diyl group, a 9,9-difluorofluoren-2,7-diyl group, or a 1,4-phenylene group in which any hydrogen is substituted with a halogen atom, a cyano group, a methyl group or trifluoromethyl group; Z1 and Z2 each independently represent a single bond, —COO—, —OCO—, —CH2CH2—, or —C≡C—; X5 and X6 each independently represent a single bond or —O—; q independently indicates 1 or 0; o, p and r each independently indicate an integer of from 0 to 20.

### Claim 16 (depends on 15)

The liquid-crystal composition as claimed in claim 15, which contains at least one compound of formula (1) and at least one polymerizable compound selected from the group of compounds of formula (M1) and (M2).

### Claim 17 (depends on 15)

The liquid-crystal composition as claimed in claim 15, which contains at least one compound of formula (1) and at least one polymerizable compound selected from the group of compounds of formula (M3).

### Claim 18 (depends on 15)

liquid-crystal composition as claimed in claim 15, which contains at least one compound of formula (1) and at least one polymerizable compound selected from the group of compounds of formulae (M4) and (M5).

### Claim 19 (depends on 15)

The liquid-crystal composition as claimed in claim 15, which contains at least one compound of formula (1) and at least one polymerizable compound selected from the group of compounds of formula (M1), (M2) and (M3).

### Claim 20 (depends on 1)

A polymer obtained by polymerizing the compound of claim 1.

### Claim 21 (depends on 11)

A polymer obtained by polymerizing the composition of claim 11.

### Claim 22 (depends on 20)

An optically-anisotropic shaped article comprising the polymer of claim 20.

### Claim 23 (depends on 22)

A liquid-crystal display device comprising the optically-anisotropic shaped article of claim 22.