# US 2014/0192305 A1 · Photoreactive compounds

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- Number: US 2014/0192305 A1
- Document ID: US20140192305A1
- Status: Published application
- Kind: A1
- Application number: 14/237,270
- Filed: 2012-08-07
- Published: 2014-07-10
- Earliest claimed: 2011-08-25
- Assignees: Rolic AG
- Inventors: Frederic Lincker; Izabela Bury S. Pires; Sabrina Chappellet; Patricia Scandiucci De Freitas; Mohammed Ibn-Elhaj; Qian Tang; Satish Palika; Masato Hoshino; Jean-Francois Eckert
- Web page: https://patentgrep.com/patent/US20140192305A1

## CPC

- G02F 1/133711: {by organic films, e.g. polymeric films}
- C07C 255/41: the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
- C07D 307/81: Radicals substituted by nitrogen atoms not forming part of a nitro radical
- C07D 317/46: condensed with one six-membered ring
- C07D 319/08: condensed with carbocyclic rings or ring systems
- C09K 19/56: Aligning agents
- C09K 2019/0448: {the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate}
- C09K 2019/0496: {the special bonding being a specific pi-conjugated group}
- C09K 2323/02: Alignment layer characterised by chemical composition
- 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
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

The present invention relates to photoreactive compounds that are particularly useful in materials for the alignment of liquid crystals.

## Claims

### Claim 1

A compound comprising a group terminal group of formula (I)
wherein:
A1 and A2 each independently are a ring system of 5 to 40 atoms, wherein each ring system includes at least one unsaturation directly connected via electron conjugation (□-□ bonding) to the double bond shown in formula (I); and wherein and A2 is linked to a polymerizable group by a single bond or at least one spacer unit;
R1 is hydrogen, a substituent L, hydroxy or a straight-chain or branched, substituted or unsubstituted C1-C12alkyl, in which one or more C-atom, CH— or CH2— group is unreplaced or replaced by a linking group;
and wherein if
W is hydrogen and Z is an electron withdrawing group, then
R4, R5 are hydrogen, and R2 and R3 are independently from each other an electron-donating single substituent, or R2 and R3 form together the residue of an electron-donating ring which is condensed to ring A1; or
if W is hydrogen and Z is an electron withdrawing group, then
R4, R5 are independently from each other a substituent L, which is halogen, hydroxy and/or a polar group; or, an electron-donating single substituent, or R4, R5 form together the residue of an electron-donating ring which is condensed to ring A2, then R2 and R3 form together the residue of an electron-donating ring which is condensed to ring A1;
or if W is an electron withdrawing group and Z is hydrogen, then
R4, R5 are independently from each other hydrogen, a substituent L, an electron-donating single substituent, or R4, R5 form together the residue of an electron-donating ring which is condensed to ring A2 or hydrogen, and R2 and R3 are independently from each other an electron-donating single substituent, or form together the residue of an electron-donating ring which is condensed to ring A1.

### Claim 2

A compound comprising a terminal group of formula (Ia)
wherein:
the doted line means a linkage of the terminal group to the residue of the compound;
A1 and A2 each independently are a ring system of 5 to 40 atoms, wherein each ring system includes at least one unsaturation directly connected via electron conjugation (□-□ bonding) to the double bond shown in formula (I); and wherein A2 is linked to a polymerizable group by a single bond or at least one spacer unit;
R1 is hydrogen, a substituent L or a straight-chain or branched, substituted or unsubstituted C1-C12alkyl, in which one or more C-atom, CH— or CH2— group is unreplaced or replaced by a linking group;
and wherein if
W is hydrogen and Z is an electron withdrawing group, then
R4, R5 are hydrogen, and R2 and R3 are independently from each other an electron-donating single substituent, preferably these electron-donating single substituents are in meta-position to each other; or
R2 and R3 form together the residue of an electron-donating ring which is condensed to ring A1; or
if W is hydrogen and Z is an electron withdrawing group, then
R4, R5 are independently from each other hydrogen, a substituent L, or an electron-donating single substituent, with the proviso that at least one R4 or R5 is a substituent L, or an electron-donating single substituent; or R4, R5 form together the residue of an electron-donating ring which is condensed to ring A2; and,
R2 and R3 form together the residue of an electron-donating ring which is condensed to ring A1; or
R4 is —O—C2-C6alkyl, such as —O-ethyl, —O-propyl, —O-butyl, —O-pentyl, —O-hexyl, R5 is hydrogen and R2 and R3 are hydrogen or an electron-donating single substituent, preferably both R2 and R3 are an electron-donating single substituent; or
R4, R5 are independently from each other a substituent L, an electron-donating single substituent, or hydrogen; and R2 and R3 are independently from each other —O—C2-C6alkyl, such as —O-ethyl, —O-propyl, —O-isopropyl, —O-butyl, —O-tert-butyl, —O-sec-butyl, —O-pentyl, —O-isopentyl, —O-hexyl; or
R4, R5 are independently from each other a —O—C2-C6alkyl, such as —O-ethyl, —O-propyl, —O-isopropyl, —O-butyl, —O-tert-butyl, —O-sec-butyl, —O-pentyl, —O-isopentyl, —O-hexyl or hydrogen, and R2 and R3 are independently from each other —O—C2-C6alkyl, such as —O-ethyl, —O-propyl, —O-isopropyl, —O-butyl, —O-tert-butyl, —O-sec-butyl,
—O-pentyl, —O-isopentyl, —O-hexyl; or
R4, R5 are independently from each other a substituent L, an electron-donating single substituent, preferably R4, R5 are O—C1-C6alkyl, more preferably —O-methyl, —O-ethyl, and R2 and R3 are independently from each other —O—C1-C6alkyl, such as —O-methyl,
—O-ethyl, —O-propyl, —O-isopropyl, —O-butyl, —O-tert-butyl, —O-sec-butyl, —O-pentyl, —O-isopentyl, —O-hexyl;
or if W is an electron withdrawing group and Z is hydrogen, then
R4, R5 are independently from each other hydrogen, a substituent L, an electron-donating single substituent, or R4, R5 form together the residue of an electron-donating ring which is condensed to ring A2 or hydrogen, and R2 and R3 are independently from each other an electron-donating single substituent, or form together the residue of an electron-donating ring which is condensed to ring A1;
most preferred is
W is hydrogen and Z is an electron withdrawing group, then
R4, R5 are hydrogen, and R2 and R3 are independently from each other an electron-donating single substituent, preferably these electron-donating single substituents are in meta-position to each other; or
R2 and R3 form together the residue of an electron-donating ring which is condensed to ring A1; or
if W is hydrogen and Z is an electron withdrawing group, then
R4, R5 are independently from each other hydrogen, a substituent L, or an electron-donating single substituent, with the proviso that at least one R4 or R5 is a substituent L, or an electron-donating single substituent; or R4, R5 form together the residue of an electron-donating ring which is condensed to ring A2; and,
R2 and R3 form together the residue of an electron-donating ring which is condensed to ring A1; or
or if W is an electron withdrawing group and Z is hydrogen, then
R4, R5 are independently from each other hydrogen, a substituent L, an electron-donating single substituent, or R4, R5 form together the residue of an electron-donating ring which is condensed to ring A2 or hydrogen, and R2 and R3 are independently from each other an electron-donating single substituent, or form together the residue of an electron-donating ring which is condensed to ring A1.

### Claim 3 (depends on 1)

The compound comprising a group terminal group of formulae (I) or (Ia) according to claim 1, wherein the polymerizable group is “D”, which is preferably selected from acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether and ester, allyl ether and ester epoxy, styrene and styrene derivatives, for example alpha-methylstyrene, p-methylstyrene, p-tert-butyl styrene, p-chlorostyrene, etc., siloxanes, diamines, imide monomers, amic acid monomers and their esters, amidimide monomers, maleic acid and maleic acid derivatives, for example, di-n-butyl maleate, dimethyl maleate, diethyl maleate, etc, fumaric acid and fumaric acid derivatives, for example, di-n-butyl fumarate, di-(2-ethylhexyl) fumarate, etc, urethanes or their corresponding homo- and co-polymers.

### Claim 4 (depends on 1)

The compound comprising a group terminal group of formulae (I) or (Ia) according to claim 1, wherein the spacer unit is S1 and/or S2 each independently from each other represents a single bond or a cyclic, straight-chain or branched, substituted or unsubstituted C1-C24alkylen, in which one or more, preferably non-adjacent, C-atom, CH— or CH2—, group unreplaced or replaced by a linking group, and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (V):
—(Z2a)a4—(Z1—C1)a1—(Z2—C2)a2—(Z1a)a3— (V)
wherein:
C1, C2 each independently represents a alicyclic or aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, preferably connected to each other via the bridging groups Z1 and/or Z2 and/or Z1a and/or Z2a, preferably C1 and C2 are connected at the opposite positions via the bridging groups Z1 and Z2 and/or Z1a and/or Z2a, so that groups S1 and/or S2 have a long molecular axis, and
Z1, Z2, Z1a, Z2a each independently represents a bridging group within the above given meanings and preferences, and
a1, a2, a3, a4 each independently represents an integer from 0 to 3, such that
a1+a2+a3+a4≦6, preferably a3 and a4 are 0 and a1+a2≦4.

### Claim 5 (depends on 1)

The compound according to claim 1 which are part of an oligomer, a dendrimer or a polymer, which may be a homopolymer or a copolymer.

### Claim 6 (depends on 1)

An oligomer, dendrimer, copolymer or polymer comprising at least one compound according to claim 1 in its polymerized form as monomer unit.

### Claim 7 (depends on 6)

The oligomer, dendrimer, copolymer or polymer according to claim 6 further comprising additives such as silane-containing compounds, epoxy-containing crosslinking agents, a photosensitiser, a photoradical generator and/or a cationic photoinitiator.

### Claim 8 (depends on 6)

The oligomer, dendrimer, copolymer or polymer according to claim 6 further comprising in admixture other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers and/or photoactive monomers.

### Claim 9 (depends on 6)

The oligomer, dendrimer, copolymer or polymer according to claim 6 which is applied to a support and reacted by irradiation with aligning light.

### Claim 10 (depends on 6)

A composition comprising an oligomer, dendrimer, copolymer or polymer according to claim 6.

### Claim 11 (depends on 6)

Use of one or more oligomers, dendrimers, copolymer or polymers according to claim 6 as an alignment layer for liquid crystals, preferably polymerizable liquid crystals or switchable liquid crystals.

### Claim 12 (depends on 6)

An alignment layer comprising one or more oligomers, dendrimers, copolymer or polymers claim 6.

### Claim 13 (depends on 12)

The alignment layer according to claim 12 having a pattern of different alignment directions.

### Claim 14 (depends on 12)

A method for the preparation of an alignment layer according to claim 12, wherein one or more of the oligomers, dendrimers, copolymer or polymers, preferably in solution, is applied to a support, which is optionally provided with an electrode, and optionally after prior imidisation, said applied oligomers, dendrimers or polymers are reacted by irradiation with aligning light and optionally subsequently bringing into contact said alignment layer with a composition comprising polymerizable liquid crystals.

### Claim 15 (depends on 14)

The method according to claim 14 wherein the alignment direction is controlled by photoalignment methods.

### Claim 16 (depends on 12)

Optical and electro-optical unstructured or structured constructional elements preferably liquid crystal display cells, multi-layer and hybrid layer elements comprising at least one alignment layer according to claim 12.

### Claim 17 (depends on 16)

Optical and electro-optical unstructured or structured constructional elements according to claim 16, represented by multilayer systems, or devices for the preparation of a display waveguide, a security or brand protection element, a bar code, an optical grating, a filter, a retarder, a compensation film, a reflectively polarizing film, an absorptive polarizing film, an anisotropically scattering film compensator and retardation film, 3-D retarder, a twisted retarder film, a cholesteric liquid crystal film, a guest-host liquid crystal film, a monomer corrugated film, a smectic liquid crystal film, a polarizer, a piezoelectric cell, a thin film exhibiting non linear optical properties, a decorative optical element, a brightness enhancement film, a component for wavelength-band-selective compensation, a component for multi-domain compensation, a component of multiview liquid crystal displays, an achromatic retarder, a polarization state correction/adjustment film, a component of optical or electro-optical sensors, a component of brightness enhancement film, a component for light-based telecommunication devices, a G/H-polarizer with an anisotropic absorber, a reflective circular polarizer, a reflective linear polarizer, a MC (monomer corrugated film), twisted nematic (TN) liquid crystal displays, hybrid aligned nematic (HAN) liquid crystal displays, electrically controlled birefringence (ECB) liquid crystal displays, supertwisted nematic (STN) liquid crystal displays, optically compensated birefringence (OCB) liquid crystal displays, pi-cell liquid crystal displays, in-plane switching (IPS) liquid crystal displays, fringe field switching (FFS) liquid crystal displays; (PSVA) polymer stabilised vertically aligned; (FPA) field-induced photo-reactive alignment; hybrid FPA; vertically aligned (VA), preferably (MVA=multidomain vertical alignment), (PVA) patterned VA; VA-IPS mode or liquid crystal displays, or displays using blue phase liquid crystals; all above display types are applied in either transmissive or reflective or transflective mode.

### Claim 18 (depends on 2)

The compound comprising a group terminal group of formulae (I) or (Ia) according to claim 2, wherein the polymerizable group is “D”, which is preferably selected from acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether and ester, allyl ether and ester epoxy, styrene and styrene derivatives, for example alpha-methylstyrene, p-methylstyrene, p-tert-butyl styrene, p-chlorostyrene, etc., siloxanes, diamines, imide monomers, amic acid monomers and their esters, amidimide monomers, maleic acid and maleic acid derivatives, for example, di-n-butyl maleate, dimethyl maleate, diethyl maleate, etc, fumaric acid and fumaric acid derivatives, for example, di-n-butyl fumarate, di-(2-ethylhexyl)fumarate, etc, urethanes or their corresponding homo- and co-polymers.

### Claim 19 (depends on 2)

The compound comprising a group terminal group of formulae (I) or (Ia) according to claim 2, wherein the spacer unit is S1 and/or S2 each independently from each other represents a single bond or a cyclic, straight-chain or branched, substituted or unsubstituted C1-C24alkylen, in which one or more, preferably non-adjacent, C-atom, CH— or CH2—, group unreplaced or replaced by a linking group, and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (V):
—(Z2a)a4—(Z1—C1)a1—(Z2—C2)a2—(Z1a)a3— (V)
wherein:
C1, C2 each independently represents a alicyclic or aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, preferably connected to each other via the bridging groups Z1 and/or Z2 and/or Z1a and/or Z2a, preferably C1 and C2 are connected at the opposite positions via the bridging groups Z1 and Z2 and/or Z1a and/or Z2a, so that groups S1 and/or S2 have a long molecular axis, and
Z1, Z2, Z1a, Z2a each independently represents a bridging group within the above given meanings and preferences, and
a1, a2, a3, a4 each independently represents an integer from 0 to 3, such that
a1+a2+a3+a4≦6, preferably a3 and a4 are 0 and a1+a2≦4.

### Claim 20 (depends on 2)

The compound according to claim 2 which are part of an oligomer, a dendrimer or a polymer, which may be a homopolymer or a copolymer.

### Claim 21 (depends on 2)

An oligomer, dendrimer, copolymer or polymer comprising at least one compound according to claim 2 in its polymerized form as monomer unit.

### Claim 22 (depends on 21)

The oligomer, dendrimer, copolymer or polymer according to claim 21 further comprising additives such as silane-containing compounds, epoxy-containing crosslinking agents, a photosensitiser, a photoradical generator and/or a cationic photoinitiator.

### Claim 23 (depends on 21)

The oligomer, dendrimer, copolymer or polymer according to claim 21 further comprising in admixture other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers and/or photoactive monomers.

### Claim 24 (depends on 21)

The oligomer, dendrimer, copolymer or polymer according to claim 21 which is applied to a support and reacted by irradiation with aligning light.

### Claim 25 (depends on 21)

A composition comprising an oligomer, dendrimer, copolymer or polymer according to claim 21.

### Claim 26 (depends on 21)

Use of one or more oligomers, dendrimers, copolymer or polymers according to claim 21 as an alignment layer for liquid crystals, preferably polymerizable liquid crystals or switchable liquid crystals.

### Claim 27 (depends on 21)

An alignment layer comprising one or more oligomers, dendrimers, copolymer or polymers claim 21.

### Claim 28 (depends on 27)

The alignment layer according to claim 27 having a pattern of different alignment directions.

### Claim 29 (depends on 27)

A method for the preparation of an alignment layer according to claim 27, wherein one or more of the oligomers, dendrimers, copolymer or polymers, preferably in solution, is applied to a support, which is optionally provided with an electrode, and optionally after prior imidisation, said applied oligomers, dendrimers or polymers are reacted by irradiation with aligning light and optionally subsequently bringing into contact said alignment layer with a composition comprising polymerizable liquid crystals.

### Claim 30 (depends on 29)

The method according to claim 29 wherein the alignment direction is controlled by photoalignment methods.

### Claim 31 (depends on 27)

Optical and electro-optical unstructured or structured constructional elements preferably liquid crystal display cells, multi-layer and hybrid layer elements comprising at least one alignment layer according to claim 27.

### Claim 32 (depends on 31)

Optical and electro-optical unstructured or structured constructional elements according to claim 31, represented by multilayer systems, or devices for the preparation of a display waveguide, a security or brand protection element, a bar code, an optical grating, a filter, a retarder, a compensation film, a reflectively polarizing film, an absorptive polarizing film, an anisotropically scattering film compensator and retardation film, 3-D retarder, a twisted retarder film, a cholesteric liquid crystal film, a guest-host liquid crystal film, a monomer corrugated film, a smectic liquid crystal film, a polarizer, a piezoelectric cell, a thin film exhibiting non linear optical properties, a decorative optical element, a brightness enhancement film, a component for wavelength-band-selective compensation, a component for multi-domain compensation, a component of multiview liquid crystal displays, an achromatic retarder, a polarization state correction/adjustment film, a component of optical or electro-optical sensors, a component of brightness enhancement film, a component for light-based telecommunication devices, a G/H-polarizer with an anisotropic absorber, a reflective circular polarizer, a reflective linear polarizer, a MC (monomer corrugated film), twisted nematic (TN) liquid crystal displays, hybrid aligned nematic (HAN) liquid crystal displays, electrically controlled birefringence (ECB) liquid crystal displays, supertwisted nematic (STN) liquid crystal displays, optically compensated birefringence (OCB) liquid crystal displays, pi-cell liquid crystal displays, in-plane switching (IPS) liquid crystal displays, fringe field switching (FFS) liquid crystal displays; (PSVA) polymer stabilised vertically aligned; (FPA) field-induced photo-reactive alignment; hybrid FPA; vertically aligned (VA), preferably (MVA=multidomain vertical alignment), (PVA) patterned VA; VA-IPS mode or liquid crystal displays, or displays using blue phase liquid crystals; all above display types are applied in either transmissive or reflective or transflective mode.