# US 8,784,684 B2 · Polymerizable compound, polymerizable liquid crystalline composition, macromolecular compound and film

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- Number: US 8,784,684 B2
- Document ID: US8784684B2
- Status: Granted
- Kind: B2
- Application number: 13/961,014
- Filed: 2013-08-07
- Published: 2013-12-05
- Granted: 2014-07-22
- Earliest claimed: 2011-03-16
- Assignees: FUJIFILM Corporation
- Applicants: FUJIFILM Corporation
- Inventors: Satoshi Shimamura; Mitsuyoshi Ichihashi
- Web page: https://patentgrep.com/patent/US8784684B2

## CPC

- C07D 265/22: Oxygen atoms
- C09K 2323/00: Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K 2323/03: Viewing layer characterised by chemical composition
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

A compound which has a benzoxazinone ring and an aromatic ring that directly bonds to the benzoxazinone ring, and has a mesogenic core substituted by a substituent having a polymerizable functional group is excellent in terms of durability, colorless, and exhibits a high Δn while having an azomethine bond.

## Claims

### Claim 1

A compound which has a benzoxazinone ring and an aromatic ring that directly bonds to the benzoxazinone ring, and has a mesogenic core substituted by a substituent having a polymerizable functional group, which is represented by the following formula (I):
wherein each of R1 and R2 independently represents a hydrogen atom, a halogen, NO2, CN, NCS, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms (here, among —CH2— that configure the alkyl group, one —CH2— or two or more non-adjacent —CH2— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —C≡C—, —CONR3—, —NR3CO— or —NR3—) or P-Sp-L-, and at least one of R1 and R2 is P-Sp-L-;
P represents a polymerizable functional group;
Sp represents a single bond or an alkylene group having 1 to 12 carbon atoms (here, among non-terminal —CH2— that configure the alkylene group, one non-terminal —CH2— or two or more non-adjacent non-terminal —CH2— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —C≡C—, —CONR4—, —NR4CO— or —NR4—);
L represents —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CONR5—, —NR5CO—, —NR5— or a single bond; when Sp is a single bond, L is also a single bond;
each of A1 and A2 independently represents a 1,4-phenylene group; one or two or more hydrogen atoms in the 1,4-phenylene group may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of Z1 and Z2 independently represents —COO—, —OCO—, —CONR6—, —NR6CO—, —OCH2—, —CH2O—, —CH2S—, —SCH2—, —CH2CH2— or a single bond;
each of X1, X2, X3, X4, X5, X6 and X7 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of R3, R4, R5 and R6 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
each of m and n independently represents 0, 1 or 2, and m+n=1 or 2.

### Claim 2 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), when m=n=1, Z1 is —COO—, and Z2 is —OCO—.

### Claim 3 (depends on 2)

The compound according to claim 2, wherein, in the formula (I), X3 is a hydrogen atom or a methoxy group.

### Claim 4 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), when m=0 and n=1, Z2 is —OCO—.

### Claim 5 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), when m=1 and n=0, Z1 is —COO—.

### Claim 6 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), P is a methacrylate group, an acrylate group, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro ortho ester group or a vinyloxy group.

### Claim 7 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), P is a polymerizable functional group selected from a group consisting of groups represented by the following formulae (P-1) to (P-5):
wherein, in the formulae, each of R11 to R13 independently represents a hydrogen atom or a methyl group.

### Claim 8 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), P is a methacrylate group or an acrylate group.

### Claim 9 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), Sp is an alkylene group having 2 to 8 carbon atoms.

### Claim 10 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), Sp is an alkylene group having 3 to 6 carbon atoms.

### Claim 11 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), each of R1 and R2 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms in which one CH2 or two or more non-adjacent CH2 may be substituted by —O— or —OCOO—, or P-Sp-L-.

### Claim 12 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), R1 and R2 are a group represented by P-Sp-L-.

### Claim 13 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), L is —O— or —OCOO—.

### Claim 14 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), each of Z1 and Z2 is —COO— or —OCO—.

### Claim 15 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), each of X1, X2, X3, X4, X5, X6 and X7 is a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, an alkoxy group having 1 or 2 carbon atoms or a halogen atom.

### Claim 16 (depends on 1)

The compound according to claim 1, wherein, in the formula (I), each of X1, X2, X3, X4, X5, X6 and X7 is a hydrogen atom, a methyl group, a methoxy group or a chlorine atom.

### Claim 17

A polymerizable liquid crystalline composition containing a compound and a chiral agent, wherein the compound has a benzoxazinone ring and an aromatic ring that directly bonds to the benzoxazinone ring, and has a mesogenic core substituted by a substituent having a polymerizable functional group, wherein the compound is represented by the following formula (I):
wherein each of R1 and R2 independently represents a hydrogen atom, a halogen, NO2, CN, NCS, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms (here, among —CH2— that configure the alkyl group, one —CH2— or two or more non-adjacent —CH2— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —C≡C—, —CONR3—, —NR3CO— or —NR3—) or P-Sp-L-, and at least one of R1 and R2 is P-Sp-L-;
P represents a polymerizable functional group;
Sp represents a single bond or an alkylene group having 1 to 12 carbon atoms (here, among non-terminal —CH2— that configure the alkylene group, one non-terminal —CH2— or two or more non-adjacent non-terminal —CH2— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —C≡C—, —CONR4—, —NR4CO— or —NR4—);
L represents —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CONR5—, —NR5CO—, —NR5— or a single bond; when Sp is a single bond, L is also a single bond;
each of A1 and A2 independently represents a 1,4-phenylene group; one or two or more hydrogen atoms in the 1,4-phenylene group may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of Z1 and Z2 independently represents —COO—, —OCO—, —CONR6—, —NR6CO—, —OCH2—, —CH2O—, —CH2S—, —SCH2—, —CH2CH2— or a single bond;
each of X1, X2, X3, X4, X5, X6 and X7 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of R3, R4, R5 and R6 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
each of m and n independently represents 0, 1 or 2, and m+n=1 or 2.

### Claim 18

A macromolecular compound obtained by polymerizing a compound which has a benzoxazinone ring and an aromatic ring that directly bonds to the benzoxazinone ring, and has a mesogenic core substituted by a substituent having a polymerizable functional group, wherein the compound is represented by the following formula (I):
wherein each of R1 and R2 independently represents a hydrogen atom, a halogen, NO, CN, NCS, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms (here, among —CH2— that configure the alkyl group, one —CH2— or two or more non-adjacent —CH2— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —C≡C—, —CONR3—, —NR3CO— or —NR3—) or P-Sp-L-, and at least one of R1 and R2 is P-Sp-L-;
P represents a polymerizable functional group;
Sp represents a single bond or an alkylene group having 1 to 12 carbon atoms (here, among non-terminal —CH2— that configure the alkylene group, one non-terminal —CH2— or two or more non-adjacent non-terminal —CHz— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —C≡C—, —CONR4—, —NR4CO— or —NR4—);
L represents —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CONR5—, —NR5CO—, —NR5— or a single bond; when Sp is a single bond, L is also a single bond;
each of A1 and A2 independently represents a 1,4-phenylene group; one or two or more hydrogen atoms in the 1,4-phenylene group may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of Z1 and Z2 independently represents —COO—, —OCO—, —CONR6—, —NR6CO—, —OCH2—, —CH2O—, —CH2S—, —SCH2—, —CH2CH2— or a single bond;
each of X1, X2, X3, X4, X5, X6 and X7 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of R3, R4, R5 and R6 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
each of m and n independently represents 0, 1 or 2, and m+n=1 or 2.

### Claim 19

A film using a compound which has a benzoxazinone ring and an aromatic ring that directly bonds to the benzoxazinone ring, and has a mesogenic core substituted by a substituent having a polymerizable functional group, wherein the compound is represented by the following formula (I):
wherein each of R1 and R2 independently represents a hydrogen atom, a halogen, NO2, CN, NCS, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms (here, among —CH2— that configure the alkyl group, one —CH2— or two or more non-adjacent —CH2— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —C≡C—, —CONR3—, —NR3CO— or —NR3—) or P-Sp-L-, and at least one of R1 and R2 is P-Sp-L-;
P represents a polymerizable functional group;
Sp represents a single bond or an alkylene group having 1 to 12 carbon atoms (here, among non-terminal —CH2— that configure the alkylene group, one non-terminal —CH2— or two or more non-adjacent non-terminal —CH2— may be substituted by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —C≡C—, —CONR4—, —NR4CO— or —NR4—);
L represents —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CONR5—, —NR5CO—, —NR5— or a single bond; when Sp is a single bond, L is also a single bond;
each of A1 and A2 independently represents a 1,4-phenylene group; one or two or more hydrogen atoms in the 1,4-phenylene group may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of Z1 and Z2 independently represents —COO—, —OCO—, —CONR6—, —NR6CO—, —OCH2—, —CH2O—, —CH2S—, —SCH2—, —CH2CH2— or a single bond;
each of X1, X2, X3, X4, X5, X6 and X7 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group or a halogen atom;
each of R3, R4, R5 and R6 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
each of m and n independently represents 0, 1 or 2, and m+n=1 or 2.