KR20190067847A

KR20190067847A - Photo-oriented copolymer material

Info

Publication number: KR20190067847A
Application number: KR1020197013263A
Authority: KR
Inventors: 사브리나 샤플레; 프레데릭 랭께
Original assignee: 롤릭 테크놀로지스 아게
Priority date: 2016-10-11
Filing date: 2017-09-29
Publication date: 2019-06-17
Also published as: TW201823317A; JP2019531398A; CN109804306A; WO2018069071A1

Abstract

The present invention relates to a siloxane copolymer comprising at least one monomer of the formula (I) and one monomer of the formula (II), for use in the photo-alignment of liquid crystals, in particular for the planar orientation of liquid crystals, And their use for electro-optical devices.

Description

Photo-oriented copolymer material

The present invention relates to a photo-alignment copolymer of liquid crystal, crosslinkable liquid crystal or non-crosslinkable liquid crystal, such as for planar orientation of liquid crystal or vertical orientation of liquid crystal. The invention also relates to compositions comprising said copolymers and their use for optical and electro-optical devices such as liquid crystal devices (LCD).

Some photo-orienting materials are already known in the art, but it is still desired to develop new photo-orienting materials with better optical quality, for example for use in electro-optical applications. The homopolymer has limited flexibility in fine-tuned chemical and / or electro-optical properties. Therefore, formulations or formulations are often constructed that should allow access to the desired chemical and / or electro-optical properties. However, there are disadvantages due to solubility problems, phase separation, heterogeneity on the surface of the orientation layer and change in electro-optical properties, which is not preferable. In order to avoid these disadvantages, there is a need for a novel photo-alignment material which solves these problems and also exhibits the desired chemical and / or electro-optical properties. One example of such a photo-oriented copolymer material is described in WO 2013/017467 A1.

The present invention discloses novel photo-oriented copolymers comprising at least a first monomer having a side chain of formula (I) and a second monomer having a side chain of formula (II) or (III). These photo-oriented copolymers have excellent optical properties, which allow access to economical manufacturing processes and low energy consumption LCDs without reducing the required optical properties.

A first object of the present invention is to provide a compound of formula (I)

Lt; RTI ID = 0.0 > (II) < / RTI >

Or (III)

Wherein the polymer backbone is a polysiloxane. &Lt; RTI ID = 0.0 > A < / RTI >

A second object of the present invention is to provide a composition comprising at least one of said copolymer and a second polymer or copolymer different from said first copolymer, and optionally an additive.

A third object of the present invention is to provide an orientation layer comprising one of said copolymers.

A fourth object of the present invention is to provide a method for producing an orientation layer comprising the copolymer, and an orientation layer obtained by such a method.

A fifth object of the present invention is to provide a method of aligning a liquid crystal for a liquid crystal display, such as for in-plane switching (IPS), for vertical alignment (VA), for twisted nematic alignment Or for the orientation of liquid crystals comprising polymerizable liquid crystals, or for the orientation of liquid crystals sandwiched between a pair of said alignment layers.

A sixth object of the present invention is to provide a method of manufacturing a liquid crystal display comprising the photo-alignment material or the alignment layer.

A seventh object of the present invention is to provide an optical or electro-optical unstructured or structured element comprising the copolymer or the orientation layer.

Accordingly, the present invention provides, in the first aspect, a first monomer having a side chain of the formula (I) and a second monomer having a side chain of the formula (II) or (III) for photo alignment of liquid crystals, Wherein the polymer backbone is a polysiloxane, wherein:

[Wherein,

n ₀ is an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1;

n ₁ is an integer of 0 to 15, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 5, most preferably 1 to 3, most preferably n ₁ is 1;

n ₂ is an integer of 0 to 15, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 5, most preferably 1 to 3, most preferably n ₂ is 1;

n ₃ is an integer of 1 to 15, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 5, most preferably 1 to 3, most preferably n ₃ is 1;

Each of X and Y independently represents H, F, Cl, CN;

S ₂ is a cyclic, aromatic, straight-chain or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, especially C ₁ -C ₁₂ alkylene, more especially C ₁ -C ₈ alkylene, more especially C ₁ -C ₆ alkylene, in particular the C ₁ -C ₄ alkyl represents a alkylene, most particularly C ₁ -C ₂ alkylene, in which one or more -C-, -CH-, -CH ₂ - may be replaced by a linking group, and , More than one -C-, -CH-, -CH ₂ - group is replaced, the linking groups may be the same or different;

E represents O, S, NH, C (C ₁ -C ₆ alkyl), NR ¹² , OC, OCOC, OCONH, OCONR ⁴ , SCS, SC wherein R ¹² is cyclic, Substituted or unsubstituted C ₁ -C ₂₄ alkyl, wherein one or more -C-, -CH-, -CH ₂ - group (s) may be replaced independently of each other by a linking group; Or preferably E is selected from the group consisting of -O-, -CO-, -COO-, -OCO-, -OOC-, S or NH;

A represents halogen or substituted or unsubstituted C ₁ -C ₂₄ alkyl, substituted or unsubstituted C ₁ -C ₂₄ alkenyl, substituted or unsubstituted C ₁ -C ₂₄ alkynyl or carboxylic acid, wherein one or more -C-, -CH-, -CH ₂ - groups may be replaced independently of one another a hetero atom; Preferably A is a halogen, H, or C ₁ -C ₂₄ alkoxy or a carboxylic acid, and; Most preferably A is H, F, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or carboxylic acid;

Z ₂ represents a chemical group having delignification of its electron density and / or inducing delocalization of the electron density of adjacent atoms thereof;

T represents a single bond, unsubstituted or substituted, straight-chain C ₁ -C ₁₆ alkyl;

* Represents the attachment site to the polymer backbone;

The second monomer has a side chain of formula (II): < RTI ID = 0.0 >

[Wherein,

E ₁ is -O-, -CO-, -COO-, -OCO-, -NR ⁸ -, -NR ⁸ CO-, -CONR ⁸ -, -NR ⁸ COO-, -OCONR ⁸ -, -NR ⁸ CONR ⁸ -, -C = C-, -C = C-, -O-COO-; Here, R ⁸ is a hydrogen atom or lower alkyl. Preferably, the crosslinking group is selected from -O-, -CO-, -COO-, -OCO-, -C = C-, -C≡C-, -O-COO-. More preferably, the crosslinking group is selected from the group consisting of -O-, -CO-, -COO-, -OCO-, -OOC-;

S ₃ is a single bond, a straight or branched C ₁ -C ₂₄ alkylene which is unsubstituted or substituted by cyano or halogen, preferably an alkyl having 1 to 16, more preferably 1 to 12 carbon atoms Wherein at least one CH ₂ group is independently of each other a heteroatom, or a heteroatom selected from the group consisting of -O-, -CO-, -COO-, -OCO-, -NR ⁸ -, -NR ⁸ CO-, -CONR ⁸ -, -NR ⁸ COO-, -OCONR ⁸ -, -NR ⁸ CONR ⁸ -, -C = C-, -C≡C-, -O-COO- Can be replaced; Here, R ⁸ is a hydrogen atom or lower alkyl. More preferably, at least one CH ₂ group is a heteroatom or a group consisting of -O-, -CO-, -COO-, -OCO-, -C = C-, -C≡C-, -O-COO- , Most preferably one CH ₂ group is replaced by a heteroatom, more preferably one CH ₂ group is replaced by oxygen;

Y ₁ and X ₁ independently of _one another are cyano or hydrogen;

Ar ₁ and Ar ₂ independently represent a ring system of 5 to 40 atoms, wherein each ring system is linked directly to a double bond of formula (II) via an electron conjugate (π-π bond) Or more unsaturation;

Wherein the ring system may be unsubstituted or substituted by one or more substituents selected from the group consisting of halogen atoms, hydroxyl groups and / or polar groups such as nitro, nitrile or carboxyl groups, and / Chain or branched alkyl residues having from 1 to 30 carbon atoms, wherein at least one, preferably non-adjacent, -CH ₂ - group is independently -O-, -CO- -CO-O -, -O-CO-, -NR ⁹ -, -NR ⁹ -CO-, -CO-NR ⁹ -, -NR ⁹ -CO-O-, -O-CO-NR ⁹ -, -NR ⁹ -CO -NR-, -CH = CH-, -C≡C-, -O-CO-O- and _{-Si (CH 3) 2 -O-} Si (CH 3) 2 -, is selected from an aromatic or alicyclic group And R ⁹ is a hydrogen atom or lower alkyl; Acryloyloxy, alkoxycarbonyloxy, alkyloxycarbonyloxy, methacryloyloxy, vinyl, allyl, and the like, having from 1 to 20 carbon atoms and preferably from 1 to 10 carbon atoms, , Vinyloxy and / or an allyloxy group;

R ₁ , R ₂ , R ₃ and R ₄ are independently of each other hydrogen, C ₁ -C ₁₂ alkoxy, halogen, straight or branched, halogen substituted or unsubstituted C ₁ -C ₂₄ alkyl; Nitrile; or

R ₁ and R ₄ are hydrogen and R ₂ and R ₃ together form a residue of an electron-donating ring which is condensed to the ring Ar ₂ ;

R ₅ , R ₆ and R ₇ independently of one another are hydrogen, C ₁ -C ₁₂ alkoxy, halogen; Straight or branched, halogen substituted or unsubstituted C ₁ -C ₂₄ alkyl; Nitrile; Or an electron-donating single substituent; or

R ₅ and R ₆ together form a moiety of an electron-donating ring which is condensed to the Ar ₁ ring;

n ₅ and n ₆ independently represent an integer of 0 to 2;

* Represents the attachment site to the polymer backbone;

The polymer backbone is a polysiloxane.

In the context of the present invention, the term "copolymer" refers to a polymer having a polymer backbone, wherein the polymer backbone can be the same or different and the side chains of the copolymer are different. The copolymer according to the present invention comprises at least one first monomer having a side chain of the formula (I) and a second monomer having a side chain of the formula (II) or (III). The copolymers according to the invention may be linear, branched or crosslinked. The term copolymer also has the meaning of a co-oligomer.

The copolymers according to various non-limiting embodiments herein may be used in the form of alternating copolymers, cyclic copolymers, random copolymers, statistical copolymers, block copolymers, graft copolymers, linear copolymers, May have polymeric or oligomeric forms of co-polymers, hyperbranched copolymers, dendritic copolymers, styrene copolymers, brush copolymers and comb-like polymers. The copolymers according to the invention may have the same or different polymer backbone. In a preferred embodiment, the copolymers of the present invention have the same polymer backbone, and the monomers differ in their side chains. In a preferred embodiment, the copolymer according to the invention comprises at least one first monomer having a side chain according to formula (I) and at least one second monomer having a side chain according to formula (II) or (III). The order and arrangement of the side chains is not limited to any preferred embodiment. Thus, the copolymer may have polymer chains having only monomers having the side chains of formula (I), and these chains are connected to other chains having only monomers having side chains of formula (II) or (III). These linkages or forms may be as defined above. Alternatively, the copolymer according to the present invention may have one or more monomers having side chains of formula (I) and one or more monomers having side chains of formula (II) or (III), wherein the monomers are randomly arranged . In certain non-limiting embodiments, the copolymer may comprise polymer chains in which the different compartments may have different forms, for example, a random polymer compartment and a block polymer compartment. The formation of the copolymer having at least one of the above-mentioned forms can be carried out in the presence of an addition polymerization, a step-growth polymerization, a condensation polymerization, a controlled living polymerization, an anionic polymerization, a cationic polymerization, a photopolymerization, a radical polymerization, a reversible addition- RTI ID = 0.0 > (RAFT) < / RTI > and metathesis polymerization.

The term "linking group ", as used in the context of the present invention, is preferably an unsubstituted or substituted alicyclic group, preferably cyclohexylene, or an unsubstituted or substituted aromatic group, a single bond, a heteroatom, -CO-, -CO-O-, -O-CO-, -N =, -CN, -NR ¹⁰ -, -NR ¹⁰ CO -, -CO-NR ¹⁰ -, -NR ¹⁰ -CO-O-, -O-CO-NR ¹⁰ -, -NR ¹⁰ -CO-NR ¹⁰ -, -CH = O-CO-O-, and _{-Si (CH 3) 2 -O-} Si (CH 3) 2 - is selected from (R ¹⁰ represents a hydrogen atom or a C ₁ -C ₆ alkyl);

However, the oxygen atoms of the connecting group are not directly connected to each other.

The substituent of the substituted alicyclic or aromatic group of the linking group may be one or more and is preferably a halogen such as fluoro, chloro, bromo, iodo, and preferably fluoro and chloro, and more preferably fluoro ; Or C ₁ -C ₆ alkoxy, such as preferably methoxy, or trifluoromethyl.

Wording "each ring system includes at least one unsaturation that is through electronic conjugation (π-π bonding) directly to the double bond", each of the ring systems Ar ₁ and Ar _2, a double of the formula (II) Quot; is understood to indicate that it contains one or more unsaturated bonds, i.e., double bonds, which are directly connected to the bond to extend the electron conjugate.

In a preferred embodiment, the ring systems Ar ₁ and Ar ₂ are monocyclic rings of 4 to 6 atoms, or 2 or more adjacent monocyclic rings of 5 or 6 atoms, or 8, 9 or 10 atoms A fused bicyclic ring system, or a carbocyclic or heterocyclic ring system selected from a fused tricyclic ring system of 13 or 14 atoms.

More preferably, the ring systems Ar ₁ and Ar ₂ are selected from pyrimidine, pyridine, thiophenylene, furanylene, phenanthrylene, naphthylene or phenylene.

More preferably, the ring system Ar ₁ is selected from pyrimidine, pyridine, pyridine cation, thiophenylene, furanylene, phenanthrylene, 9,10-dihydrophenanthrene, pyrene, naphthylene, 9H- 9-dimethyl-9H-fluorene or phenylene, and A1 is selected from the group consisting of cyclohexane, cyclohexene, cyclohexadiene, pyrimidine, pyridine, thiophenylene, furanylene, phenanthryl Naphthylene or phenylene, or an adjacent aromatic and / or aromatic / cycloaliphatic group in the form of a steroid skeleton or a rod.

In yet another embodiment,

Ar < ₁ > is a ring system of formula (IV)

Ar ₂ is a ring system of formula (V):

[Wherein:

Each of C ¹ and C ² is independently a substituted or unsubstituted non-aromatic, or optionally substituted aromatic, of 3 to 40 atoms connected to each other at opposite positions through a bridging group Z ¹ and Z ² , to 14 carbocyclic or heterocyclic group of atoms, and the substituted C ^1, the substituents of C ² is R ^5, R for the ring Ar ₁ ⁶ or R ⁷ and the ring R ^1, for Ar ₂ R ^2, R ³ or R < ⁴ >

Z ^3, Z ⁴ each independently represent a single bond or -CH (OH) -, -O-, -CH 2 (CO) -, -SO-, -CH 2 (SO) -, -SO 2 -, - _{CH 2 (SO 2) -,} -COO-, -OCO-, -COF 2 -, -CF 2 CO-, -S-CO-, -CO-S-, -SOO-, -OSO-, -CH 2 _{-CH 2 -, -O-CH 2} -, -CH 2 O-, -CH = CH-, -C≡S-, -SH = CH-COO-, -OCO-CH = CH-, -CH = N -, -C (CH ₃ ) ═N-, -O-CO-O-, -N═N-, a group selected from short alkyl spacers of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms ego;

a is 0, 1, 2 or 3, preferably a is 0 or 1, more preferably 0;

With the proviso that C ² directly connected to the double bond is unsaturated and conjugated thereto.

The term "linked to each other at opposite positions through the bridging groups Z ³ and Z ⁴ " means that the 5- and 6-membered rings are not 1,3- or 1,4 - means to be connected in position. Similar connection patterns in other, e.g. higher-membered, rings will be apparent to those skilled in the art.

The ring system Ar ₂ is understood to have a structure similar to the ring system Ar ₁ of the formula (IV) except that the group Ar ₂ has a terminal group. Thus, when a = 0, the group C ² represents the terminal group, and when a> 0, the group C ¹ is connected via the bridge Z ⁴ , and the final group C ¹ is the terminal group. Thus, when a = 1, the ring system A ² has the formula:

Similarly, when a = 2 or 3, the ring system A ² has the formula:

Preferably, C ¹ , C ² in formulas (IV) and (V) independently of one another have one of the following meanings:

[Wherein,

L is selected from the group consisting of halogen, hydroxyl and / or polar groups such as nitrile, cyano or carboxy, and / or acryloyloxy, alkoxy such as methoxy, ethoxy, propoxy, alkylcarbonyloxy, alkyloxycarbonyl Substituted or unsubstituted with fluorine and / or chlorine, and / or a silane group, and / or a siloxane group, such as methoxy, ethoxy, methacryloyloxy, vinyl, vinyloxy, allyl, allyloxy, and / (Wherein the alkyl moiety has from 1 to 20 C-atoms and the at least one, preferably non-adjacent, CH ₂ group is independently -O-, -CO-, -CO-O-, O-CO-, -CH = CH-, -C≡C-, -O-CO-O-, Si (CH ₃ ) ₂ -O-Si (CH ₂ ) ₂ - , Preferably L is methoxy, halogen, CF ₃ or hydrogen;

u1 is 0, 1, 2, 3 or 4;

u2 is 0, 1, 2 or 3;

u3 is 0, 1 or 2;

More preferably, C ¹ and C ² are phenanthryl, phenanthrylene, biphenyl, biphenylene, naphthyl, naphthylene, cyclohexyl, cyclohexylene, phenyl or phenylene, pyridine, pyridinylene; Preferably naphthyl or naphthylene, phenyl or phenylene, pyridine or pyridinylene.

Preferably, each of Z ³ and Z ⁴ in formulas (IV) and (V) is independently a single bond or most preferably -CH (OH) -, -O-, -CH ₂ (CO) -COO-, -OCO-, -COF ₂ -, -CF ₂ CO-, -CH ₂ -CH ₂ -, -O-CH ₂ -, -CH ₂ O-, -CH = CH-, -OCO-CH = CH-, -CH = N-, -C (CH 3) = N-, -O-CO-O-, -N = N-, or 1 to 6 carbon atoms, preferably 1 to 3 carbon Lt; / RTI > is a bridging group selected from short alkyl spacers having an atom.

More preferably, each of Z ³ and Z ⁴ is independently a single bond, -O-, -CH ₂ (CO) -, -COO-, -OCO-, -CH ₂ -CH ₂ -, -OCO- CH-, -N = N-, or a short alkyl spacer of 1 to 3 carbon atoms.

In the context of the present invention, the electron-donating ring which is condensed to the ring Ar ₂ is preferably an unsubstituted or substituted -X ² -C ₁ -C ₂₄ alkylene- (X ³ ) _{0 or 1} - unsubstituted or substituted -X ^₂ -C ² -C ₂₄ alkylene - (X ³⁾ _{0 or} ₁ - (X ² and X ³ is a single bond, independently of each other, -O-, -S-, Se, -N- , -NH- and -NR ₁₁ , R ₁₁ is a hydrogen atom or a linear or branched alkyl or alkylene group having from 1 to 12, more preferably from 1 to 6 carbon atoms, and at least one, preferably at least one, The non-adjacent -CH ₂ -groups can not be independently substituted or are preferably -O-, -CO-, -CO-O-, -O-CO-, -C = C-, More preferably R ₁₁ is a hydrogen atom or methyl, or preferably R ₁₁ is optionally substituted C ₁ -C ₆ alkyl, more preferably R ₁₁ is hydrogen ); Within the above-indicated preferred ranges, substituted -X ² -C ₁ -C ₂₄ alkylene- (X ³ ) _{0 or 1} - is preferably methyl or ethyl substituted with C ₁ -C ₂₄ alkylene, Is the same C ₁ -C ₆ alkyl. Preferred X ² and X ³ are the same, more preferably X ² and X ³ are -O-. Another preferred -X ² -C ₁ -C ₂₄ alkylene- (X ³ ) _{0 or 1} - is -X ² -C ₁ -C ₁₂ alkylene- (X ³ ) _{0 or 1} -, more preferably -X ² -C ₁ -C ₆ alkylene- (X ³ ) _{0 or 1} -, and most preferably -X ² -C ₁ -C ₃ alkylene- (X ³ ) _{0 or 1} -, in particular 1, 3-propylene, 1,2-ethylene, _{methylene, -CH (CH 3) CH (} CH 3) -, -CH 2 CH (CH 3) CH 2 - is. More preferred X ¹ and X ² are the same and are selected from -O-propylene-O-, -O-ethylene-O-, -ethylene-O-, -O-methylene-O-, -OCH (CH ₃ ) CH ₃ ) -O-, -O-CH ₂ CH (CH ₃ ) CH ₂ -O-.

In the context of the present invention, the phrase " electron-donating single substituent "

C ₁ -C ₂₄ alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, isopentyl, hexyl, iso-hexyl; or

-X ⁴ -C ₁ -C ₂₄ alkyl, preferably -C ₁ -C ₁₂ alkyl ⁴ -X, more preferably -X ⁴ -C ₁ -C ₆ alkyl, most preferably -X ⁴ -C ₁ -C ₃ alkyl (X ⁴ is a single bond, -O-, -S-, Se, -N-, -NH- and -NR ₁₁ , preferably -O- and R ₁₁ is as described above ), And within the abovementioned preferred ranges; Preferably -O-methyl, -O-ethyl, -O-propyl, -O-isopropyl, -O-butyl, -O-sec.-butyl, -O-isopentyl, -O-hexyl or -O-iso-hexyl; or

-X ⁴ -C ₁ -C ₂₄ alkylene-aryl, preferably -O-benzylene, -O-methylene-phenyl, -O-ethylene-phenyl; Or -O-CF _3;

With the proviso that, in the residue C ₁ -C ₂₄ alkyl, one or more C-atoms, CH- or CH ₂ -groups can be replaced by a linking group. Preferred C ₁ -C ₂₄ alkyl residues are C ₁ -C ₁₂ alkyl, more preferably C ₁ -C ₆ alkyl, and more preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, Butyl, iso-pentyl, pentyl, hexyl or isohexyl, most preferably methyl and ethyl. The most preferred electron-donating substituent is a single methyl, ethyl, propyl, isopropyl, butyl, sec.- butyl, tert.- butyl, -O-CF _3, -O- benzyl alkylene, -O- methylene-phenyl, -O -methyl, -O- ethyl, -O- propyl, -S- methyl, ethyl -S-, -S- profile, -NR ₁₁ - methyl, -NR ₁₁ - acetate, -NR ₁₁ - propyl (R ₁₁ is hydrogen Or methyl.

In the context of the present invention, the term "polysiloxane" means any polymer, copolymer or oligomer comprising a functional group having a Si-O-Si linkage. The polysiloxanes according to the invention may be linear, branched or crosslinked. The polysiloxane is synthesized by methods well known in the art.

Most preferred are polysiloxane skeletons comprising monomers of the formula:

[Wherein,

R _a represents OH, Cl, a substituted or unsubstituted alkoxyl group having 1 to 20 carbons, an alkyl group having 1 to 20 carbons, or an aryl group having 1 to 20 carbons;

S ₁ is a single bond or a straight or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, especially C ₁ -C ₁₂ alkylene, more particularly C ₁ -C ₈ alkylene, more especially C ₁ -C ₆ alkyl Most preferably C ₁ -C ₄ alkylene, most especially C ₁ -C ₂ alkylene (in which one or more -C-, -CH-, and CH ₂ - groups may be replaced by a linking group);

z is an integer of 0 to 15, preferably 1 to 10, more preferably 1 to 8, more preferably 1 to 5, still more preferably 1 to 3, most preferably n is 1;

Z ₁ is a single bond or a substituted or unsubstituted aliphatic or alicyclic ring having ₃ to ₁₂ carbon atoms, more preferably ₃ to ₁₀ carbon atoms, more preferably ₅ to ₈ carbon atoms, and most preferably ₅ to ₆ carbon atoms. Lt; / RTI >

R ₀ is OH, Cl, a linear or branched, substituted or unsubstituted alkoxyl group having from 1 to 20 carbons (-C-, -CH-, -CH ₂ - is an unsubstituted or substituted C ₆ -C ₂₀ aryl group Lt; / RTI > may be substituted;

* Represents the attachment site to the side chain.

Preferred are those comprising monomers according to formula (VI) wherein Z ₁ represents a substituted or unsubstituted C ₅ -C ₆ cycloaliphatic group and S ₁ represents substituted or unsubstituted C ₁ -C ₂₄ straight chain alkyl. &Lt; / RTI > More preferred is a polymer having a polymer skeleton containing a monomer according to the formula (VI) (wherein Z ₁ represents a substituted or unsubstituted cyclohexanol group or a substituted or unsubstituted cyclohexane ether group and S ₁ represents an ethyl group) Polysiloxane.

The polysiloxane backbone comprising monomers according to formula (VI) is a polymer chain which may be linear, branched or crosslinked. The polymer chain is substituted one or more times in the side chain of formula (I) and is substituted at least once in the side chain of formula (II) or (III). At least one other monomer of the polysiloxane skeleton of the polysiloxane skeleton containing monomers according to formula (VI) is replaced by a side chain of formula (I) and the monomer according to formula (VI) ) Or (III), all the siloxane monomers of the polysiloxane skeleton containing monomers according to formula (VI) are not necessarily replaced with side chains.

In the copolymers according to the invention, the polymer backbone may comprise the same or different polymer backbones comprising monomers according to formula (VI).

In the context of the present invention, the term "alkyl" includes both straight and branched alkyl, as well as saturated and unsaturated groups. The term "alkyl" has the meaning of unsubstituted or substituted alkyl, wherein substituted alkyl also has the meaning of alkylene. As used in the context of the present invention, alkyl, alkyloxy, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkylene, alkyloxycarbonyloxy, alkyl acryloyloxy Methacryloyloxy, alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy, and alkylallyloxy and alkyleneoxyalkyl groups such as methacryloyloxyalkyl, methacryloyloxyalkyl, methacryloyloxyalkylene, alkylmethacryloyloxy, Each represent an alkyl residue, an alkylene residue thereof, a cyclic, linear or branched, substituted or unsubstituted alkyl, and an alkylene, respectively, wherein one or more, preferably non-adjacent- -CH- or -CH ₂ - groups may be replaced, or, or may be replaced by a linking group, and preferably can be replaced by -O-, NH, -COO, OCO.

Also, in the context of the present invention, "alkyl" refers to a branched or straight chain, unsubstituted or substituted alkyl, preferably C ₁ -C ₄₀ alkyl, especially C ₁ -C ₃₀ alkyl, preferably C ₁ -C ₂₀ Alkyl, more preferably C ₁ -C ₁₆ alkyl, most preferably C ₁ -C ₁₀ alkyl and most particularly preferably C ₁ -C ₆ alkyl. Thus, alkylenes are, for example, C ₁ -C ₄₀ alkylenes, especially C ₁ -C ₃₀ alkylenes, preferably C ₁ -C ₂₀ alkylenes, more preferably C ₁ -C ₁₆ alkylenes, Preferably C ₁ -C ₁₀ alkylene and especially most preferably C ₁ -C ₆ alkylene.

In the context of the present invention, the definition of alkyl given below applies analogously to alkylene.

C ₁ -C ₆ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl or hexyl.

C ₁ -C ₁₀ alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl,

C ₁ -C ₁₆ alkyl is for example methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Tridecyl, tetradecyl, pentadecyl or hexadecyl.

C ₁ -C ₂₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, tert.- butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.

C ₁ -C ₂₄ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, tert.- butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.

C ₁ -C ₃₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, tert.- butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, But are not limited to, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henecosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, Or triacontyl.

C ₁ -C ₄₀ alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, tert.- butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, But are not limited to, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henecosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, , Triacontyl or tetraconyl.

C ₁ -C ₆ alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec.-butoxy, tert.-butoxy, pentoxy or hexoxy.

C ₁ -C ₂₀ acryloyloxyalkylene, preferably C ₁ -C ₁₀ acryloyloxyalkylene, C ₁ -C ₆ acryloyloxyalkylene is, for example, acryloyloxymethylene, acrylic Acryloyloxypropylene, acryloyloxybutylene, acryloyloxy-sec.-butylene, acryloyloxypentylene, acryloyloxyhexylene, acryloyloxypropylene, acryloyloxypropylene, acryloyloxybutylene, acryloyloxy- Acryloyloxyhexylene, acryloyloxydecylene, acryloyloxyundecylene, acryloyloxydecylene, acryloyloxytridecylene, acryloyloxytridecylene, acryloyloxyoctylene, acryloyloxyoctylene, acryloyloxydecylene, Acryloyloxyhexadecylene, acryloyloxyheptadecylene, acryloyloxyoctadecylene, acryloyloxynonadecylene, acryloyloxy eicosylene, acryloyloxyhexadecylene, acryloyloxyhexadecylene, acryloyloxyhexadecylene, .

C ₁ -C ₂₀ methacryloyloxyalkylene, preferably C ₁ -C ₁₀ methacryloyloxyalkylene, C ₁ -C ₆ methacryloyloxyalkylene is, for example, methacryloyloxy Methacryloyloxypropylene, methacryloyloxybutylene, methacryloyloxy-sec-butylene, methacryloyloxyphenylene, methacryloyloxyphenylene, methacryloyloxyphenylene, methacryloyloxyphenylene, methacryloyloxyphenylene, Acrylonitrile, methacryloyloxyhexylene, methacryloyloxyundecylene, methacryloyloxyundecylene, methacryloyloxyundecylene, methacryloyloxyhexylene, methacryloyloxyhexylene, methacryloyloxyhexylene, methacryloyloxyhexylene, methacryloyloxyundecylene, methacryloyloxyundecylene, methacryloyloxyhexylene, Methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, methacryloyloxyheptadecylene, Methacryloyloxynodecylenes, methacryloyloxyacetylenes, methacryloyloxydecylenes, methacryloyloxyadecylenes, A xylene.

C ₁ -C ₂₀ acryloyloxyalkoxy, preferably C ₁ -C ₁₀ acryloyloxyalkoxy, C ₁ -C ₆ acryloyloxyalkoxy is, for example, acryloyloxy methoxy, acryloyloxyalkoxy, Acryloyloxypolyoxy, acryloyloxypolyoxy, acryloyloxypropoxy, acryloyloxyisopropoxy, acryloyloxybutoxy, acryloyloxy-sec.-butoxy, acryloyloxypentoxy, acryloyloxyhexoxy, acryloyloxyhexoxy, Acryloyloxydecoxy, acryloyloxydodecoxy, acryloyloxydodecoxy, acryloyloxydodecoxy, acryloyloxydodecoxy, acryloyloxydodecoxy, acryloyloxydodecoxy, acryloyloxymethyloxyoctyloxy, to be.

C ₁ -C ₂₀ methacryloyloxyalkoxy, preferably C ₁ -C ₁₀ methacryloyloxyalkoxy, C ₁ -C ₆ methacryloyloxyalkoxy is, for example, methacryloyloxymethoxy , Methacryloyloxyethoxy, methacryloyloxypropoxy, methacryloyloxyisopropoxy, methacryloyloxybutoxy, methacryloyloxy-sec.-butoxy, methacryloyloxyphene, methacryloyloxyphenoxy, Methoxy, ethoxy, methacryloyloxyhexyloxy, methacryloyloxyheptoxy, methacryloyloxyoctoxy, methacryloyloxynoxyl, methacryloyloxydecoxy, methacryloyloxy undecoxy , Methacryloyloxydecanoic acid, methacryloyloxytridecyloxy.

Aliphatic groups can be, for example, saturated or unsaturated, mono-, non-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca- valent alkyl, alkylene, alkyloxy, alkyl (Meth) acryloyloxy, acryloyloxy, alkyl acrylate, alkyl methacrylate, alkyl (phenylene) acryl, Alkoxy, alkylvinyloxy, or alkylallyloxy, which may contain one or more heteroatoms and / or bridging groups.

The alicyclic group is preferably a non-aromatic group or a unit and may be substituted or unsubstituted. Preferably, the alicyclic group is a non-aromatic carbocyclic or heterocyclic group, for example a cyclic group having from 3 to 30 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclo Hexane, cyclohexene, cyclohexadiene, decalin, tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroid skeleton such as cholesterol. A preferred cycloaliphatic group is cyclohexane. Substituents on alicyclic groups are C ₁ -C ₆ alkoxy, preferably methoxy or trifluoro, substituted or unsubstituted with halogen, which leads to the formation of a halogen, preferably fluoro and / or chloro, or an ether group Methyl or one or more hydroxyl groups. Preferred is a cyclohexanol group or a cyclohexane group substituted by C ₁ -C ₆ alkoxy, which is referred to in the context of the present invention, as the cyclooate group.

The term "aromatic ", as used in the context of the present invention, refers to an unsubstituted or substituted carbocyclic and heterocyclic group preferably containing 5, 6, 10 or 14 ring atoms, Benzene or phenylene, pyridine, pyrimidine, naphthalene, which may form a cyclic group such as biphenylene or triphenylene, at least a single heteroatom and / or at least a single bridging group is not inserted or inserted; Or fused polycyclic systems such as phenanthrene, tetralin. Preferably, the aromatic group is benzene, phenylene, biphenylene or triphenylene. More preferred aromatic groups are benzene, phenylene and biphenylene. Particularly preferred substituents of the aromatic group or the carbocyclic and heterocyclic groups are halogen, preferably fluoro and / or chloro, C ₁ -C ₆ alkoxy, preferably methoxy or trifluoromethyl.

The carbocyclic or heterocyclic aromatic or alicyclic group may be substituted with one or more groups selected from, for example, aziridine, epoxy, cyclopropyl, furan, pyrrolidine, oxazoline, imidazole, benzene, pyridine, triazine, pyrimidine, naphthalene, , Biphenylene or tetralin units, preferably naphthalene, phenanthrene, biphenylene or phenylene, more preferably naphthalene, biphenylene or phenylene, and most preferably phenylene, preferably 3, 4, 5, 6, 10 or 14 ring atoms.

Particularly preferred substituents of carbocyclic and heterocyclic aromatic or alicyclic groups are halogen, preferably fluoro and / or chloro, C ₁ -C ₆ alkoxy, preferably methoxy or trifluoromethyl.

An unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic group is, for example, unsubstituted or mono- or poly-substituted. Preferred substituents on the carbocyclic or heterocyclic aromatic group are one or more trifluoromethyl, halogen such as fluoro, chloro, bromo, iodo, especially fluoro and / or chloro, and more especially fluoro; Hydroxyl, polar group, acryloyloxy, alkyl acryloyloxy, alkoxy, especially methoxy, ethoxy, propoxy; Alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxycarbonyloxy, methacryloyloxy, vinyl, vinyloxy and / or an allyloxy group, wherein the alkyl moiety preferably has 1 to 20 carbon atoms , And more preferably 1 to 10 carbon atoms. Preferred polar groups are nitro, nitrile or carboxy groups, and / or cyclic, linear or branched C ₁ -C ₃₀ alkyl, which are unsubstituted or mono- or poly-substituted. Preferred substituents for C ₁ -C ₃₀ alkyl are methyl, fluorine and / or chlorine, wherein one or more, preferably non-adjacent -C-, -CH-, -CH ₂ - groups are independently replaced by a linking group . Preferably, the linking group is selected from -O-, -CO-, -COO- and / or -OCO-.

Monocyclic rings of 5 or 6 atoms are, for example, furan, benzene, preferably phenylene, pyridine, pyrimidine, pyridine cations, pyrimidine cations.

The bicyclic ring system of 8, 9 or 10 atoms is, for example, naphthalene, biphenylene or tetralin.

The 13 or 14 atomic tricyclic ring system is, for example, phenanthrene.

As used in the context of the present invention, the term "phenylene" preferably denotes a 1,2-, 1,3- or 1,4-phenylene group which is optionally substituted. Particularly preferred substituents of phenylene are halogen, preferably fluoro and / or chloro, C ₁ -C ₆ alkoxy, preferably methoxy or trifluoromethyl. The phenylene group is preferably a 1,3- or 1,4-phenylene group. Particularly preferred is a 1,4-phenylene group.

The term "halogen" denotes a chloro, fluoro, bromo or iodo substituent, preferably a chloro or fluoro substituent, and more preferably fluoro.

The term "heteroatom ", as used in the context of the present invention, refers to a neutral, anionic or cationic heteroatom and is predominantly oxygen, sulfur and nitrogen, halogen such as fluoro, chloro, bromo, iodo, Preferably fluoro and / or chloro, and most preferably fluoro; Preferably in the form of halogen, oxygen and nitrogen, in the latter case primary amines, secondary amines, tertiary amines or quaternary ammonium cations, preferably -NH-.

The term "optionally substituted" as used in the context of the present invention is mainly a lower alkyl, such as C ₁ -C ₆ alkyl, lower alkoxy, such as C ₁ -C ₆ alkoxy, hydroxy, halogen, for example fluorine or chlorine , Or a polar group such as a cyano group.

Alkyl, alkoxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl, acryloyloxyalkylene, alkyloxycarbonyloxy, alkyl acryloyloxy, methacryloyloxy, With respect to the alkyl group, the alkyl group, the alkyl group, the alkyl group, the alkoxy group, the alkyl group, the alkoxy group, the alkyl group, the alkoxy group, , -CH-, -CH ₂ - or a part of several groups, for example, a hetero atom, as well as, it is pointed out repeatedly, that other group, preferably a cross-linking group can be replaced. In this case, it is generally preferred that these substituents are not directly connected to each other. Alternatively, heteroatoms, and especially oxygen atoms, are preferably not directly connected to each other.

In a preferred embodiment, the first aspect of the present invention relates to a copolymer for photo-alignment of liquid crystals, in particular for planar orientation of liquid crystals, which comprises at least one monomer having side chains of formula (I)

[Wherein,

n ₀ , n ₁ , n ₂ , n ₃ , S ₂ , A, and T are as described above;

E represents O, or S or NH;

X and Y are H;

Z ₂ Is CN;

* Represents the attachment site to the polymer backbone; And

A second monomer having a side chain of formula (II):

[Wherein,

E ₁ , n ₅ , n ₆ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as described above;

One of X < _{1 >} or Y < ₁ > is cyano and the other is hydrogen;

S ₃ is a straight or branched C ₁ -C ₂₄ alkylene, more preferably a C ₁ -C ₁₂ alkylene, more preferably a C ₄ -C ₁₂ alkylene, wherein one or more -CH ₂ - independently represent a hetero atom, or a -O-, -CO-, -COO-, -OCO-, -NR 8 each other ^{-, -NR 8 CO-, -CONR 8} -, -NR 8 COO-, -OCONR 8 -, -NR ⁸ CONR ⁸ -, -C = C-, -C≡C-, -O-COO- (wherein R ⁸ is a hydrogen atom or lower alkyl);

* Represents the attachment site to the polymer backbone]

Wherein the polymer is a polysiloxane.

In a further preferred embodiment, the first aspect of the present invention relates to a copolymer for photo-alignment of liquid crystals, in particular a plane orientation of liquid crystals, which comprises at least one monomer having side chains of formula (I)

[Wherein,

n ₀ , n ₁ , n ₂ , n ₃ , S ₂ , T are as described above;

A represents H, one or more halogens, one or more methoxy groups or one or more carboxyl groups;

E represents O, or S or NH;

X and Y are H;

Z ₂ Is CN;

* Represents the attachment site to the polymer backbone; And

A second monomer having a side chain of formula (III):

[Wherein,

One of X < _{1 >} or Y < ₁ > is cyano and the other is hydrogen;

* Represents the attachment site to the polymer backbone]

Wherein the polymer is a polysiloxane.

In a further preferred embodiment, the first aspect of the present invention relates to a copolymer for photo-alignment of liquid crystals, in particular for planar orientation of liquid crystals, comprising one monomer having a side chain of formula (I)

[Wherein,

n ₀ , n ₁ , n ₂ , n ₃ , S ₂ , T are as described above;

A represents H, a halogen, a methoxy group or a carboxyl group;

E represents O;

X and Y are H;

Z ₂ Is CN;

* Represents the attachment site to the polymer backbone; And

A second monomer having a side chain of formula (III):

[Wherein,

One of X < _{1 >} or Y < ₁ > is cyano and the other is hydrogen;

* Represents the attachment site to the polymer backbone]

Wherein the polymer is a polysiloxane.

In a further preferred embodiment, the first aspect of the present invention relates to a copolymer for photo-alignment of liquid crystals, in particular for planar orientation of liquid crystals, which comprises one monomer having a side chain of formula (Ia)

[Wherein,

n _O and T are as described above;

A represents H, a halogen, a methoxy group or a carboxyl group;

E represents O;

X and Y are H;

Z ₂ Is CN;

* Represents the attachment site to the polymer backbone; And

A second monomer having a side chain of formula (II):

[Wherein,

One of X < _{1 >} or Y < ₁ > is cyano and the other is hydrogen;

* Represents the attachment site to the polymer backbone]

Wherein the polymer is a polysiloxane.

[Wherein,

n _O and T are as described above;

A represents H, a halogen, a methoxy group or a carboxyl group;

E represents O;

X and Y are H;

Z ₂ Is CN;

* Represents the attachment site to the polymer backbone; And

A second monomer having a side chain of formula (III):

[Wherein,

One of X < _{1 >} or Y < ₁ > is cyano and the other is hydrogen;

* Represents the attachment site to the polymer backbone]

Wherein the polymer is a polysiloxane.

[Wherein,

n _O and T are as described above;

A represents H, a halogen, a methoxy group or a carboxyl group;

E represents O;

X and Y are H;

Z ₂ Is CN;

* Represents the attachment site to the polymer backbone; And

A second monomer having a side chain of formula (III):

[Wherein,

E ₁ , n ₅ , n ₆ , S ₃ , R ₄ and R ₅ have the same meanings as described above;

One of X < _{1 >} or Y < ₁ > is cyano and the other is hydrogen;

R ₁ , R ₂ and R ₃ are independently of each other H or -CF ₃ or methoxy;

* Represents the attachment site to the polymer backbone]

Wherein the polymer is a polysiloxane.

[Wherein,

n _O and T are as described above;

A represents H, a halogen, a methoxy group or a carboxyl group;

E represents O;

X and Y are H;

Z ₂ Is CN;

* Represents the attachment site to the polymer backbone; And

A second monomer having a side chain of formula (III):

[Wherein,

One of X < _{1 >} or Y < ₁ > is cyano and the other is hydrogen;

S ₃ is C ₄ alkylene or C ₅ alkylene or C ₆ alkylene or C ₇ alkylene or C ₈ alkylene or C ₉ alkylene or C ₁₀ alkylene or C ₁₁ alkylene or C ₁₂ alkylene;

* Represents the attachment site to the polymer backbone]

Wherein the polymer is a polysiloxane.

The present invention relates to a composition comprising a first monomer having a side chain of formula (I) or (Ia) and a second monomer having a side chain of formula (II) or (III) The molar ratio of the second monomer of the formula (II) or (III) to the total amount of the monomers of the formula (II) or (III) is 0.01% to 50%, preferably 0.01% to 25%, more preferably 0.01% To 15% by weight of the copolymer.

In a second embodiment, the invention relates to a composition comprising a second polymer or copolymer different from the first copolymer and the one or more copolymers as described above.

In a second preferred embodiment, the present invention relates to a composition comprising a second polymer or copolymer and additives different from the one or more copolymers and the first copolymer as described above.

The second polymer or copolymer of the second embodiment of the present invention is a polymer or copolymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, polymerizable liquid crystal, polymerized liquid crystal (LCP), polysiloxane, Polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polyvinyl ethers, polyvinyl esters, polyallyl ethers, polyallyl esters, polystyrenes, polyamideimides, polymaleic acids, polyfumaric acids, polyurethanes and A derivative thereof, a derivative thereof, a derivative thereof, a polystyrol, a polyester, a polyurethane, a polyethylene, a polypropylene, a polyvinyl chloride, a polytetrafluoroethylene, a polycarbonate, a polysilane, a polymaleinimide, a polynorbornene, Stilbene and dendrimer.

A more preferred second polymer or copolymer of the second embodiment of the present invention is a polyamic acid or polyimide. The most preferred is polyamic acid.

It is to be understood that the term " diamine "or" diamine compound "refers to a chemical structure that has two or more amino groups, i.e., can also have three or more amino groups.

When the second polymer or copolymer is a diamine, the diamine represents an optionally substituted aliphatic, aromatic or alicyclic diamino group having 1 to 40 carbon atoms, preferably aniline, p-phenylenediamine, m-phenyl The compounds listed or selected from the group of structures of lenediamine, benzidine, diaminofluorene, or derivatives thereof, provided that the listed compounds having no two amino groups are referred to as derivatives having at least one additional amino group, (E.g., Aldrich, ABCR, ACROS, Fluka), which may also be used as a comonomer, preferably as a comonomer, such as the following commercially available amino compounds:

4-Amino-2,3,5,6-tetrafluorobenzoic acid

4-Amino-3,5-diiodobenzoic acid

3,4-diaminobenzoic acid

4-Amino-3-methylbenzoic acid

4-Amino-2-chlorobenzoic acid

4-Aminosalicylic acid

4-aminobenzoic acid

4-aminophthalic acid

1- (4-aminophenyl) ethanol

4-aminobenzyl alcohol

4-Amino-3-methoxybenzoic acid

4-aminophenylethylcarbinol

4-Amino-3-nitrobenzoic acid

4-Amino-3,5-dinitrobenzoic acid

4-Amino-3,5-dichlorobenzoic acid

4-amino-3-hydroxybenzoic acid

4-aminobenzyl alcohol hydrochloride

4-Aminobenzoic acid hydrochloride

Pararosaniline base

4-Amino-5-chloro-2-methoxybenzoic acid

4- (Hexafluoro-2-hydroxyisopropyl) aniline

Piperazine-p-aminobenzoate

4-Amino-3,5-dibromobenzoic acid

Isonicotinic acid hydrazide p-amino salicylate salt

4-Amino-3,5-diiodosalicylic acid

4-Amino-2-methoxybenzoic acid

2- [2- (4-aminophenyl) -2-hydroxy-1- (hydroxymethyl) ethyl] isoindoline-

4-Amino-2-nitrobenzoic acid

2,4-diaminobenzoic acid

p-aminobenzoic acid

[3,5-3H] -4-amino-2-methoxybenzoic acid

L- (+) - threo-2-amino-1- (4-aminophenyl)

L- (+) - threo-2- (N, N-dimethylamino) -1- (4-aminophenyl)

Ethyl 2- (4-aminophenyl) -3,3,3-trifluoro-2-hydroxypropanoate

Ethyl 2- (4-amino-3-methylphenyl) -3,3,3-trifluoro-2-hydroxypropanoate

Ethyl 2- (4-amino-3-methoxyphenyl) -3,3,3-trifluoro-2-hydroxypropanoate

3,4-diaminobenzyl alcohol dihydrochloride

4-aminonaphthalene-1,8-dicarboxylic acid

4-Amino-3-chloro-5-methylbenzoic acid

4-Amino-2,6-dimethylbenzoic acid

4-Amino-3-fluorobenzoic acid

4-Amino-5-bromo-2-methoxybenzenecarboxylic acid

2,7-diaminofluorene

4,4'-diaminooctafluorobiphenyl

3,3'-diaminobenzidine

3,3 ', 5,5'-tetramethylbenzidine

3,3'-dimethoxybenzidine

o-Tolidine

3,3'-dinitrobenzidine

2-nitrobenzidine

3,3'-dihydroxybenzidine

o-Tolidine sulfone

Benzidine

3,3'-dichlorobenzidine

2,2 ', 5,5'-tetrachlorobenzidine

Benzidine-3,3'-dicarboxylic acid

4,4'-diamino-1,1'-binaphthyl

4,4'-diaminodiphenyl-3,3'-diglycolic acid

Dihydroeti

o-dianisidine

2,2'-Dichloro-5,5'-dimethoxybenzidine

3-methoxybenzidine

3,3'-dichlorobenzidine (diphenyl-d6)

2,7-diamino-9-fluorenone

3,5,3 ', 5'-tetrabromo-biphenyl-4,4'-diamine

2,2'-bis (trifluoromethyl) benzidine

2,2'-dichloro [1,1'-biphenyl] -4,4'-diamine

3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo (a, c) cyclohepten-

3,3'-bis (trifluoromethyl) benzidine

Dibenzo (1,2) dithiene-3,8-diamine

3,3'-Tolidine-5-sulfonic acid

3,3'-dichlorobenzidine-d6

Tetramethylbenzidine

3,3'-diaminobenzophenone

3,3'-diaminodiphenylmethane

4,4-Bis- (3-amino-4-hydroxyphenyl) -valeric acid

2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

2,2-bis (3-amino-4-methylphenyl) hexafluoropropane

Tetrabromomethylene dianiline

2,7-diamino-9-fluorenone

2,2-bis (3-aminophenyl) hexafluoropropane

Bis- (3-amino-4-chloro-phenyl) -methanone

Bis- (3-amino-4-dimethylamino-phenyl) -methanone

3- [3-Amino-5- (trifluoromethyl) benzyl] -5- (trifluoromethyl) aniline

1,5-diaminonaphthalene

Or a derivative thereof, but also an enumerated compound having no two amino groups is taken as a derivative having at least one additional amino group.

Preferred examples of further other diamines are as follows:

Ethylene diamine, 1,3-propylene diamine, 1,4-butylene diamine, 1,5-pentylene diamine, 1,6-hexylene diamine, 1,7-heptylene diamine, 1,9-nonylenediamine, 1,10-decylenediamine, 1,11-undecylenediamine, 1,12-dodecylenediamine,?,? '- diamino- Diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl) methylamine, 1,2-diaminocyclohexane, 4,4'- diaminodicyclohexylmethane, 1,3 Diaminobenzoic acid methyl ester, 3,5-diaminobenzoic acid hexyl ester, 3,5-diamino-3,5-diamino benzoic acid, Benzoic acid dodecyl ester, 3,5-diaminobenzoic acid isopropyl ester, 4,4'-methylenedianiline, 4,4'-ethylenedianiline, 4,4'-diamino-3,3'-dimethyldiphenyl Methane, 3,3 ', 5,5'-tetramethylbenzidine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene , 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4 , 4'-diamino-2,2'-dimethylbibenzyl, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4- (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,7-diaminofluorene, 9,9- (2-chloroaniline), 4,4'-bis (4-aminophenoxy) biphenyl, 2,2 ', 5,5'-tetrachloro- , 2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'- diaminobiphenyl, 4,4 ' 4-phenylene isopropylidene) bisaniline, 4,4 '- (1,3-phenylene isopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) , 2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-amino-4-methylphenyl] hexafluoropropane, 2,2- 4-aminophenyl) hexafluoropropane, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, Bis (trifluoromethyl) biphenyl, and 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -2,3,5,6,2 ' , 5 ', 6'-octafluorobiphenyl;

As well as the diamines disclosed in US 6,340,506, WO 00/59966 and WO 01/53384, all of which are expressly incorporated herein by reference.

The diamine compounds according to the present invention can be prepared using methods known to those skilled in the art.

In addition, preferred diamines are commercially available as listed below:

polymer

Poly (3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride-co-4,4'-oxydianiline / 1,3-phenylenediamine), amic acid solution

Poly (pyromellitic dianhydride-co-4,4'-oxydianiline), ammic acid solution

Aromatic diamine:

2,7-diaminofluorene

1,5-diaminoanthraquinone

2,6-diaminoanthraquinone

Pararosaniline hydrochloride

3,6-acridine diamine

4,4'-diaminooctafluorobiphenyl

2,2'-dithiodianiline

3,3 ', 5,5'-tetramethylbenzidine

3,3'-diaminodiphenyl sulfone

4,4'-diamino-2,2'-dimethylbibenzyl

4,4'-diaminodiphenyl ether

4,4'-dithiodianiline

4,4'-diaminodiphenyl sulfone

4,4'-diaminodiphenylmethane

4,4'-ethylene dianiline

3,3'-dimethoxybenzidine

2,2'-dithiobis (1-naphthylamine)

3,7-diamino-2-methoxyfluorene

3,6-diamino-10-methylacridinium chloride

Propidium iodide

o-dianisidine dihydrochloride

2,7-diaminofluorene dihydrochloride

Pararosaniline acetate

3,6-diamino-10-methylacridinium chloride hydrochloride

Proplavine dihydrochloride

o-Tolidine dihydrochloride

3,3 ', 5,5'-tetramethylbenzidine dihydrochloride

3,3'-diaminobenzidine tetrahydrochloride

4,4'-diaminostilbene dihydrochloride

4,4'-diaminodiphenylamine sulfate

Pro Flavine Art Pate

2,2'-ethylenedianiline diphosphate

1,5-diamino-4,8-dihydroxyanthraquinone

o-Tolidine

3,3'-diaminobenzophenone

3,3'-diaminodiphenylmethane

3,4'-diaminodiphenylmethane

2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane

4,4'-diamino-1,1'-dianthramide

3,3'-dinitrobenzidine

4,4'-diamino-5,5'-dimethyl-2,2'-biphenyldisulfonic acid

4,4'-diaminostilbene-2,2'-disulfonic acid

3-amino-4-hydroxyphenylsulfone

4,4-Bis- (3-amino-4-hydroxyphenyl) -valeric acid

2,2'-diamino-4,4'-difluorobibenzyl

2-amino-4-chlorophenyldisulfide

3,3 '- (decamethylene dioxy) dianiline

3,3 '- (pentamethylene dioxy) dianiline

4- (p-aminoanilino) -3-sulfoaniline

4- [3- (4-aminophenoxy) propoxy] aniline

2-nitrobenzidine

Benzidine-3-sulfonic acid

4,4'-diaminodiphenylsulfide

4,4'-diaminobenzanilide

n, n'-bis (3-aminophenylsulfonyl) ethylenediamine

2,2'-biphenyldiamine

3,4'-diaminodiphenyl ether

Pro Flavine Art Pate

Phenosapranin

4,4'-diaminobenzophenone

2,2-bis (4-aminophenyl) hexafluoropropane

2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

2,2-bis (3-amino-4-methylphenyl) hexafluoropropane

3,3'-dihydroxybenzidine

3,3'-diamino-4,4'-dihydroxybiphenyl

4,4'-bis (4-aminophenoxy) biphenyl

2,2-bis [4- (4-aminophenoxy) phenyl] propane

1,4-bis (4-aminophenoxy) benzene

1,3-bis (4-aminophenoxy) benzene

Bis [4- (4-aminophenoxy) phenyl] sulfone

9,9-bis (4-aminophenyl) fluorene

o-Tolidine sulfone

Benzidine

3,3'-dichlorobenzidine dihydrochloride

Benzidine dihydrochloride

3,6-thioxanthenediamine-10,10-dioxide

4,4'-diamino-2,2'-biphenyl disulfonic acid

4,4'-azodianiline

2,5-bis- (4-aminophenyl) - (1,3,4) oxadiazole

3,3'-dimethylnaphthidine

Benzidine sulfate

1,3-bis (3-aminophenoxy) benzene

3,3'-dichlorobenzidine

2,2 ', 5,5'-tetrachlorobenzidine

4,4'-diamino-1,1'-binaphthyl

Diamine Bordeaux

Benzoflavin

Chris Aniline

2,2'-thiobis (5-aminobenzenesulfonic acid)

4,4'-methylene-bis (2-chloroaniline)

Tetrabromomethylene dianiline

4,4'-diamino-3,3'-dinitrodiphenyl ether

Benzidine pyrophosphate

3,6-diaminothioxanthene-10-dioxide, dihcl

4,4 "-diamino-p-terphenyl

1,8-diamino-4,5-dihydroxyanthraquinone

Bis (p-aminophenoxy) dimethylsilane

Bis [4- (3-aminophenoxy) phenyl] sulfone

4,4'-methylene di-2,6-xylidine

2-aminobenzaldehyde-ethylene-diimine

3-methylbenzidine dihydrochloride

3,3'-diethylbenzidine dihydrochloride

3,6-diaminoacridine hydrochloride

Disodium 4,4'-diamino-5,5'-dimethyl-2,2'-biphenyldisulfonate

4,4'-methylenebis (3-chloro-2,6-diethylaniline)

4,4'-methylene-bis- (2,6-diethylaniline)

4,4'-methylenebis- (2,6-diisopropylaniline)

Toluylenediamine

3,8-diamino-6-phenylphenanthridine

Thionine perchlorate

Dihydroeti

Thionine

4,4-diaminobenzenesulfonyl anilide

o-dianisidine HCl

2,2'-Dichloro-5,5'-dimethoxybenzidine

3-methoxybenzidine

2,2 '- (hexamethylene dioxy) dianiline

2,2 '- (pentamethylene dioxy) dianiline

2,2 '- (Ethylenedioxy) Dianiline

4- [4- (4-aminophenoxy) butoxy] aniline

2,2'-diamino-4'-methoxy-4-methylbenzanilide

5,5'-dimethyl-2,2'-dinitrobenzidine

n, n'-bis (2-aminophenyl) -1,3-propanediamine

3,4'-diamino-chalcone

2,3 ', 4,5', 6-pentaphenyl-3,4'-biphenyldiamine

2 - ([1- (4- (1- [(2-aminophenyl) thio] -2-nitroethyl) phenyl) -2-nitroethyl] thio) aniline

2 - ((2- [(2-aminophenyl) thio] ethyl) thio) aniline

2 - ((4- [(2-aminophenyl) thio] but-2-enyl) thio) aniline

4,4'-diamino-3,3'-dimethyldiphenylmethane

2,2'-diamino-bibenzyl

Trimethylene bis (4-aminobenzoate)

Fluorescein amine

Benzidine mixture

3-nitro-4,4'-methylenedianiline

4,4-diamino-2,2'-dichlorodiphenyldisulfide

1,6-diaminopyrene

1,8-diaminopyrene

3,6-diaminocarbazole

4,4 '(5') - Diamino- [2,4] -dibenzo-18-crown-6, dihydrochloride

4,4'-diaminostilbene-2,2'-disulfonic acid, disodium salt

(r) - (+) - 2,2'-diamino-1,1'-binaphthyl

Pro Flavinhe Art Pate 2 Luggage

3,6-diaminoacridineh artpate 1/2 hydrate

Dimethyl bromide monohydrate

o-Tolylidine dihydrochloride hydrate

3,3 ', 5,5'-tetramethylbenzidine dihydrochloride hydrate

3,3'-diaminobenzidine tetrahydrochloride dihydrate

3,6-bis (4-amino-3- (sodium sulfonato) phenylamino)] - 2,5-dichloro 4-benzoquinone

2,2 ' -dimethylbenzidine hydrochloride

2,2 '- (phenylmethylenebis) bis (4-methylaniline)

3,4'-diaminobiphenyl

2,7-diamino-9-fluorenone

n, n'-bis (2-aminophenyl) oxamide

2- [2- (2-aminophenyl) diaz-1-enyl] aniline

3,5,3 ', 5'-tetrabromo-biphenyl-4,4'-diamine

n, n'-bis (4-aminophenyl) -1,3-bis (aminomethyl) benzene dihydrochloride

4 ', 4 "(5") -diaminodibenzo-15-crown-5

2,2'-bis (trifluoromethyl) benzidine

Bis (4-amino-2,3-dichlorophenyl) methane

Alpha, alpha '- bis (4-aminophenyl) -1,4-diisopropylbenzene

2,2-bis (3-aminophenyl) hexafluoropropane

3,10-diamino-6,13-dichlorobenzo [5,6] [1,4] oxazino [2,3-b] phenoxazine-4,11-disulfo

n1- (2-amino-4-methylphenyl) -2-aminobenzamide

n1- (2-amino-4-chlorophenyl) -2-aminobenzamide

2,2'-dichloro [1,1'-biphenyl] -4,4'-diamine

4,4 '(5') - diaminodibenzo-15-crown-5 dihydrochloride

rcl p19,413-1

Bis- (4-amino-3-nitro-phenyl) -methanone

Bis- (3-amino-4-chloro-phenyl) -methanone

Bis- (3-amino-4-dimethylamino-phenyl) -methanone

n, n'-bis- (4-amino-2-chloro-phenyl) -isophthalamide

n, n'-bis- (4-amino-2-chloro-phenyl) -terephthalamide

3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo (a, c) cyclohepten-

2-Aminobenzaldehyde n - [(z) - (2-aminophenyl) methylidene] hydrazone

3,3'-bis (trifluoromethyl) benzidine

Dicarboxidine 2 hcl

4,4 '- (1,3-phenylene diisopropylidene) bisaniline

1,4-phenylenebis [[4- (4-aminophenoxy) phenyl] methanone]

2 - ((5- [(2-aminophenyl) thio] -3,4-dinitro-2- thienyl) thio) aniline

n'1- (2-aminobenzoyl) -2-aminobenzene-1-carbohydrazide

2- [4- (5-amino-1 H-benzimidazol-2-yl) phenyl] -1h-benzimidazol-

4- [4- (4-aminophenoxy) -2,3,5,6-tetrafluorophenoxy] aniline

3,3'-dinitro-4,4'-diaminodiphenyl sulfone

3,3 ', 4,4'-tetraaminodiphenyl sulfone

4- [1- (4-aminophenyl) -1-methylethyl] aniline

3,3-diaminodiphenylurea

Bis (4-aminophenyl) acetylene

Dibenzo (1,2) dithiene-3,8-diamine

Ethidium homodimer-2

Bis'- (2-aminobenzenesulfonyl) bis-phenol ester

Neopentyl glycol bis (4-aminophenyl) ether

2,2'-oxydianiline

4,4'-diaminodiphenylamine-2,2-disulfonic acid

4,4-diaminodiphenylurea

3,3'-Tolidine-5-sulfonic acid

n1- (3 - [(2-aminobenzoyl) amino] propyl) -2-aminobenzamide

2 - ((6 - [(2-aminophenyl) sulfanyl] -5-nitro-2-pyridyl) sulfanyl) aniline

2 - ((6-amino-1,3-benzothiazol-2-yl) dithio) -1,3-benzothiazol-

Tetramethylbenzidine

2 - ([6- [(2-aminophenyl) sulfanyl] -3,5-di (trifluoromethyl) -2-pyridyl] sulfanyl) aniline

3,6-diaminothioxanthene-10-dioxide dihydrochloride

m-Tolridine dihydrochloride hydrate

Amino-n - [2-amino-4- (trifluoromethyl) phenyl] -5-methylbenzamide

2 - ([2- [(2-aminophenyl) thio] -6-nitro-4- (trifluoromethyl) phenyl] thio) aniline

2 - [(3 - ([(2-aminophenyl) thio] methyl) -2,4,6-trimethylbenzyl) thio] aniline

3- [3-Amino-5- (trifluoromethyl) benzyl] -5- (trifluoromethyl) aniline

2 - ((5- [(2-aminophenyl) thio] -4-chloro-2-nitrophenyl) thio) aniline

4- (1- (4-aminophenyl) -2- [4- (dimethylamino) phenyl] vinyl)

1,5-bis (4-aminophenoxy) pentane

2,3'-Dichlorobenzidine dihydrochloride

3,3'-diamino-4,4'-dichlorodiphenyl sulfone

3- (bis- (4-amino-phenyl) -methyl) -2,3-dihydro-isoindol-

4,4-diaminodiphenyl-2-sulfonic acid

4,4'-diamino-diphenylene-cyclohexane

4,5'-diamino- (1,1 ') biantracenyl-9,10,9', 10'-tetraene

Alicyclic diamine:

4,4'-methylenebis (cyclohexylamine)

4,4'-methylenebis (2-methylcyclohexylamine)

Aliphatic diamines:

1,8-diamino-p-methane

4,4'-methylenebis (cyclohexylamine)

d-cystine

l-cysteine dimethyl ester dihydrochloride

Namine

Bis (2-aminopropyl) amine

(h-cys-beta-na) 2 2 hcl

l-cystine dibenzyl ester < RTI ID = 0.0 >

1,4-diaminocyclohexane

(h-cys-pna) 2

dl-2-aminopropionic acid anhydride

cystine (di-b-naphthylamide) hydrochloride

cystine-bis-p-nitroanilide dihydrobromide

l-cystine diethyl ester dihydrochloride

Trans-1,4-cyclohexanediamine

4,4'-methylenebis (2-methylcyclohexylamine)

l-leucine thiol, oxidized dihydrochloride

1,3-diaminoamantane dihydrochloride

l-leucine thiol disulfide 2 < RTI ID = 0.0 > HC1

l-cysteine disodium salt, monohydrate

Homocysteine methyl ester hydrochloride

1,3-adamantanediamine

Tetracyclo [8.2.1.1 (8,11) .0 (2,7)] tetradeca-2,4,6-triene-10,11-diamine

Tricyclo [3.3.1.0 (3,7)] nonane-3,7-diamine.

Among the classes of commercially available diamines, preferred are listed below:

Alicyclic diamine:

4,4'-methylenebis (cyclohexylamine)

4,4'-methylenebis (2-methylcyclohexylamine)

Aliphatic diamine

4,4'-methylenebis (cyclohexylamine)

1,4-diaminocyclohexane

Trans-1,4-cyclohexanediamine

4,4'-methylenebis (2-methylcyclohexylamine)

1,3-adamantanediamine

Aromatic diamine

2,7-diaminofluorene

2,6-diaminoanthraquinone

4,4'-diaminooctafluorobiphenyl

4,4'-diaminodiphenyl ether

4,4'-dithiodianiline

4,4'-diaminodiphenylmethane

4,4'-ethylene dianiline

3,3'-dimethoxybenzidine

o-Tolidine

3,3'-diaminobenzophenone

3,3'-diaminodiphenylmethane

3,4'-diaminodiphenylmethane

2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane

4- [3- (4-aminophenoxy) propoxy] aniline

4,4'-diaminodiphenylsulfide

4,4'-diaminobenzophenone

2,2-bis (4-aminophenyl) hexafluoropropane

4,4'-bis (4-aminophenoxy) biphenyl

2,2-bis [4- (4-aminophenoxy) phenyl] propane

1,4-bis (4-aminophenoxy) benzene

1,3-bis (4-aminophenoxy) benzene

Bis [4- (4-aminophenoxy) phenyl] sulfone

9,9-bis (4-aminophenyl) fluorene

Benzidine

4,4'-azodianiline

1,3-bis (3-aminophenoxy) benzene

4,4'-diamino-1,1'-binaphthyl

4,4 "-diamino-p-terphenyl

Bis (p-aminophenoxy) dimethylsilane

4- [4- (4-aminophenoxy) butoxy] aniline

3,4'-diamino-chalcone

Trimethylene bis (4-aminobenzoate)

3,4'-diaminobiphenyl

2,7-diamino-9-fluorenone

4 ', 4 "(5") -diaminodibenzo-15-crown-5

2,2'-bis (trifluoromethyl) benzidine

Alpha, alpha '- bis (4-aminophenyl) -1,4-diisopropylbenzene

3,3'-bis (trifluoromethyl) benzidine

4,4 '- (1,3-phenylene diisopropylidene) bisaniline

1,4-phenylenebis [[4- (4-aminophenoxy) phenyl] methanone]

4- [4- (4-aminophenoxy) -2,3,5,6-tetrafluorophenoxy] aniline

4- [1- (4-aminophenyl) -1-methylethyl] aniline

Neopentyl glycol bis (4-aminophenyl) ether

4,4-diaminodiphenyl or

1,5-bis (4-aminophenoxy) pentane.

Among the classes of commercially available diamines (L), more preferred are listed below:

Aromatic diamine:

2,7-diaminofluorene

4,4'-diaminooctafluorobiphenyl

4,4'-diaminodiphenyl ether

4,4'-diaminodiphenylmethane

4,4'-ethylene dianiline

3,3'-diaminobenzophenone

4- [3- (4-aminophenoxy) propoxy] aniline

4,4'-diaminodiphenylsulfide

4,4'-diaminobenzophenone

2,2-bis (4-aminophenyl) hexafluoropropane

4,4'-bis (4-aminophenoxy) biphenyl

2,2-bis [4- (4-aminophenoxy) phenyl] propane

1,4-bis (4-aminophenoxy) benzene

1,3-bis (4-aminophenoxy) benzene

9,9-bis (4-aminophenyl) fluorene

Benzidine

Bis (p-aminophenoxy) dimethylsilane

4- [4- (4-aminophenoxy) butoxy] aniline

3,4'-diamino-chalcone

Trimethylene bis (4-aminobenzoate)

3,4'-diaminobiphenyl

2,7-diamino-9-fluorenone

4 ', 4 "(5") -diaminodibenzo-15-crown-5

4- [4- (4-aminophenoxy) -2,3,5,6-tetrafluorophenoxy] aniline

4- [1- (4-aminophenyl) -1-methylethyl] aniline

1,5-bis (4-aminophenoxy) pentane

Aliphatic diamines:

4,4'-methylenebis (cyclohexylamine)

1,4-diaminocyclohexane

Alicyclic diamine

4,4'-methylenebis (cyclohexylamine).

Preferably, the further polymer, mono- or copolymer or oligomer comprises at least one diamine as a basic building block, and a tetracarboxylic acid anhydride, preferably a tetracarboxylic acid anhydride of the formula (VII).

Preferably, the tetracarboxylic acid anhydride, which is substituted or unsubstituted, preferably substituted or unsubstituted in the polar group, has the formula (VII)

[Wherein:

T represents a tetravalent organic radical.

The tetravalent organic radical T is preferably derived from an aliphatic, alicyclic or aromatic tetracarboxylic dianhydride.

Preferred examples of aliphatic or alicyclic tetracarboxylic dianhydrides include:

1,1,4,4-butanetetracarboxylic acid dianhydride,

Ethylene maleic anhydride,

1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,2,3,4-cyclopentanetetracarboxylic acid dianhydride;

2,3,5-tricarboxycyclopentylacetic dianhydride (including all isomers of this compound, in particular exo and / or endo, by the term "2,3,5-tricarboxycyclopentylacetic acid dianhydride"), The 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride can be obtained, for example, in JP 59-190945, JP 60-13740 and JP 58-109479, DE 1078120 and JP 58-109479 , Or methods as described in GB 872,355, and JP 04458299 (these methods are incorporated herein by reference);

Tetrahydro-4,8-methanofuro [3,4-d] oxepine-1,3,5,7-tetron,

3- (carboxymethyl) -1,2,4-cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride,

Hexahydrofuro [3 ', 4': 4,5] cyclopenta [1,2-c] pyran-1,3,4,6-tetron,

3,5,6-tricarboxy norbornyl acetic acid dianhydride,

2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, rel- [1S, 5R, 6R] -3-oxabicyclo [3.2.1] octane- 3 '- (tetrahydrofuran-2', 5'-dione),

4- (2,5-dioxotetrahydrofuran-3-yl) tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride,

5- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride,

Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,

Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride,

1,8-dimethylbicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,

Pyromellitic dianhydride,

3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride,

4,4'-oxydiphthalic dianhydride,

3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride,

1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,3-difluoro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,2,3-trimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1-methyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,4,5,8-naphthalenetetracarboxylic acid dianhydride,

2,3,6,7-naphthalenetetracarboxylic acid dianhydride,

3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride,

3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride,

1,2,3,4-furan tetracarboxylic acid dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) -diphenyl sulfone dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride,

3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride,

Ethylene glycol bis (trimellitic acid) dianhydride,

4,4 '- (1,4-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (1,3-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride,

4-tert-butyl-6- (2,5-dioxotetrahydro-3-furanyl) -2-benzofuran-

(2,5-dioxotetrahydro-3-furanyl) -3a, 4,5,9b-tetrahydronaphtho [1,2- c ] furan-

(2,5-dioxotetrahydro-3-furanyl) -5-methyl-3a, 4,5,9b-tetrahydronaphtho [l, 2- c ]

5- (2,5-dioxotetrahydro-3-furanyl) -6-methylhexahydro-2-benzofuran-

5- (2,5-dioxotetrahydro-3-furanyl) -7-methyl-3a, 4,5,7a-tetrahydro-2-benzofuran-

6- (2,5-dioxotetrahydro-3-furanyl) -4-methylhexahydro-2-benzofuran-

Synthesis of 9-isopropyloctahydro-4,8-ethenopro [3 ', 4': 3,4] cyclobuta [1,2- f ] [2] benzofuran- 1,3,5,7-tetron ,

1,2,5,6-cyclooctetetracarboxylic acid dianhydride,

4 ': 3,4] cyclobuta [1,2-f] [2] benzofuran-1,3,5,7-tetrone,

Octahydrofuro [3 ', 4': 3,4] cyclobuta [1,2-f] [2] benzofuran-1,3,5,7-

Tetrahydro-3,3'-bifuran-2,2 ', 5,5'-tetron,

4,4'-oxyd (1,4-phenylene) bis (phthalic acid) dianhydride, and

4,4'-methylene di (1,4-phenylene) bis (phthalic acid) dianhydride.

Preferred examples of the aromatic tetracarboxylic dianhydride are as follows:

Pyromellitic dianhydride,

3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride,

4,4'-oxydiphthalic dianhydride,

3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride,

1,4,5,8-naphthalenetetracarboxylic acid dianhydride,

2,3,6,7-naphthalenetetracarboxylic acid dianhydride,

3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride,

3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride,

1,2,3,4-furan tetracarboxylic acid dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride,

4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride,

3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride,

Ethylene glycol bis (trimellitic acid) dianhydride,

4,4 '- (1,4-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (1,3-phenylene) bis (phthalic acid) dianhydride,

4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride,

4,4'-oxydi (1,4-phenylene) bis (phthalic acid) dianhydride,

4,4'-methylene di (1,4-phenylene) bis (phthalic acid) dianhydride,

4-tert-Butyl-6- (2,5-dioxotetrahydro-3-furanyl) -2-benzofuran-

Etc.

More preferably, the tetracarboxylic acid dianhydride used to form the tetravalent organic radical T is selected from:

1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,

1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,

2,3,5-tricarboxycyclopentylacetic acid dianhydride,

Tetrahydro-4,8-methanofuro [3,4-d] oxepine-1,3,5,7-tetron,

3- (carboxymethyl) -1,2,4-cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride,

Hexahydrofuro [3 ', 4': 4,5] cyclopenta [1,2-c] pyran-1,3,4,6-tetron,

Pyromellitic dianhydride,

Methyl-3a, 4,5,9b-tetrahydronaphtho [l, 2-c] furan-l, 3-dione,

(2,5-dioxotetrahydro-3-furanyl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-

4-tert-butyl-6- (2,5-dioxotetrahydro-3-furanyl) -2-benzofuran-

4,4 '- (hexafluoroneisopropylidene) diphthalic acid dianhydride, and

Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.

In the context of the present invention, the term "polyimide" has the meaning of a partially or fully imidized polyamic acid or polyamic acid ester. Similarly, the term "imidization" has the meaning of partial or complete imidization in the context of the present invention.

A second embodiment of the present invention more particularly relates to a composition comprising the second polymer or copolymer in an amount of 100% imidized, or 1 to 99% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% &Lt; / RTI >

In the context of the second embodiment of the invention, the composition comprises a siloxane copolymer as described above, a second polymer or copolymer different from the first copolymer, and first and second polymers or copolymers of the composition May comprise one or more additional polymers or copolymers that are different.

In a second preferred embodiment, the present invention relates to a composition comprising a second polymer or copolymer and an additive different from the one or more siloxane copolymers and first copolymers as described above, &Lt; / RTI >

Additives are selected from the group consisting of: nucleating agents, cleaning agents, antistatic agents, antioxidants, slip agents, silica, talc, stabilizers, UV stabilizers, lubricants, coupling agents, antimicrobial agents, crosslinking agents, Siloxane monomers such as acid generators, base generators or tetraalkoxy-siloxanes as tetraethoxysilane, or trialkoxy siloxanes; Surfactants, photo-activators, photo-sensitizers, photo-generators.

Additives such as silane-containing compounds and epoxy-containing cross-linking agents may be used.

Suitable silane-containing additives include Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc. Lt; / RTI >

Suitable epoxy-containing crosslinking additives include 4,4'-methylene-bis- (N, N-diglycidyl aniline), trimethylolpropane triglycidyl ether, benzene- 1,2,4,5-tetracarboxylic acid 1,2,4,5-N, N'-diglycidyldiimide, polyethylene glycol diglycidyl ether, N, N-diglycidylcyclohexylamine, and the like.

Suitable photo-activators include, but are not limited to, mixtures of 2,2-dimethoxyphenylethanone, diphenylmethanone and N, N-dimethylbenzenamine or mixtures of ethyl 4- (dimethylamino) benzoate, xanthone, Cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Irgacure ^® 500 (1 -hydroxy- Benzophenone in a 1: 1 weight ratio mixture) and 2,2-dimethoxy-1,2-diphenylethane-1-one, Michler ketone, triarylsulfonium salts and the like.

A composition, preferably a blend, according to a second embodiment of the present invention comprises a copolymer according to the definition and preferences of the present invention, a second polymer or copolymer different from the first copolymer, optionally further comprising an organic solvent . In the context of the present invention, the organic solvent means any solvent commonly known in the art. More specifically, the organic solvent is selected from the group consisting of: hydrocarbons, ketones, esters, ethers and alcohols.

Examples of such hydrocarbons include toluene and xylene; Examples of such ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone and cyclohexanone; Examples of such esters include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethyl lactate; Examples of such ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran and dioxane; Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- Glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono-n-propyl ether. Of these, water-insoluble organic solvents are preferred.

Further examples of organic solvents include chlorobenzene, pyrrolidone solvents, preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone; Imidazolidinone, dimethylsulfoxide, dimethylformamide, toluene, chloroform, organic esters such as acetyl acetic acid ester or butyl acetic acid ester, pentyl acetic acid ester, hexyl acetic acid ester; But are not limited to, additional Y-butyrolactone, methyl cellosolve, butyl cellosolve, butyl carbitol, tetrahydrofuran, diethylene glycol diethyl ether, dipentyl ether, dipropylene glycol dimethyl ether, diisobutyl ketone monoethyleneglycol dimethyl ether . These solvents may be used alone or as a mixture thereof.

The amount of the organic solvent is preferably 0.5 to 150,000 parts by weight, preferably 100 to 100,000 parts by weight, more preferably 150 to 25,000 parts by weight, based on 100 parts by weight of all the copolymer compounds.

These organic solvents may be used alone or in combination of two or more.

In the context of the present invention, the phrase "polymer or oligomer layer" has the meaning "copolymer layer or oligomer layer ".

In the context of the present invention, the phrase "orientation layer" has the same meaning as "orientation film ".

The copolymers according to the invention can be used in the form of an orientation layer alone or in combination with other polymers, copolymers, oligomers, monomers, photo-active polymers, photo-active oligomers and / May be used in combination with an active monomer. Therefore, it is understood that by changing the composition of the copolymer layer, it is possible to control specific and desired properties such as good surface wetting, high voltage retention, specific fixed energy, and the like.

A fourth object of the present invention relates to a method for producing an orientation layer comprising the copolymer by exposing the copolymer to an alignment light, and an orientation layer obtained by this method.

The copolymer comprises at least one photo-reactive group in its side chain.

Preferably, the photo-reactive groups of the side chain react by exposing to the oriented light.

In the context of the present invention, the term "photo-reactive group" has the meaning of a group capable of reacting with light, preferably by interaction with the oriented light.

The treatment with the aligned light can be performed in a single step or in several individual steps. In a preferred embodiment of the present invention, the treatment with the oriented light is performed in a single step.

In the context of the present invention, the photo-reactive group preferably has the meaning of a dimer, isomeric, polymeric and / or crosslinkable group.

In the context of the present invention, the oriented light, preferably the polarized light, is a light of a wavelength capable of initiating photo-alignment. Preferably, the wavelength is UV-A, UVB and / or UV / C range, or visible range. This depends on the photo-alignment compound, and this wavelength is appropriate. Preferably, the photo-reactive group is sensitive to visible light and / or UV light. Another embodiment of the present invention relates to the generation of oriented light by laser light.

The instantaneous direction of the aligned light may be perpendicular to the substrate, or it may be any oblique angle.

More preferably, the oriented light is at least partially linearly polarized, elliptically polarized, e.g. circularly polarized, or non-polarized light; Most preferably at least circularly or partially linearly polarized light, or obliquely exposed non-polarized light. In particular, the most preferred alignment light represents substantially polarized light, particularly linearly polarized light; Or the orientation light represents non-polarized light applied by oblique illumination.

A more preferred embodiment of the present invention relates to a method of preparing an oriented layer by exposing the copolymer to polarized light, in particular linearly polarized light, or non-polarized light by oblique irradiation.

More preferred are the following inventive copolymers:

The copolymer is a copolymer gel or copolymer network; And / or

-Copolymer has an intrinsic viscosity in the range of 0.01 to 10 dL / g, preferably in the range of 0.02 to 5 dL / g; And / or

-Copolymer has a molecular weight of 1 to 6,000,000, 1,000 to 6,000,000, 2,000 to 1,000,000, 2,000 to 500,000, more preferably 5,000 to 250,000.

- the copolymer has 2 to 20,000 repeating units, in particular 4 to 2000 repeating units, more particularly 6 to 1000 repeating units; And / or

- Copolymers or oligomers are in the form of statistical copolymers.

A more preferred embodiment of the present invention relates to a copolymer having an intrinsic viscosity preferably in the range of 0.01 to 10 dL / g, more preferably in the range of 0.01 to 1 dL / g. Herein, the intrinsic viscosity (eta inh = lnηrel / C) is calculated by the following equation, using N-methyl-2-pyrrolidone as a solvent, at a concentration of 0.5 g / 100 ml of a solution for evaluation of its viscosity at 30 DEG C Is determined by measuring the solution.

A preferred embodiment of the present invention also relates to a copolymer containing 2 to 20,000 repeating units, particularly 4 to 2000 repeating units, more particularly 6 to 1000 repeating units.

A copolymer layer can be easily prepared from the copolymer of the present invention, and another embodiment of the present invention is a copolymer layer comprising a copolymer according to the present invention, which is preferably produced by treatment with an oriented light .

Preferably, the invention relates to a copolymer layer comprising a copolymer according to the invention or as prepared according to the invention.

The copolymer layer is preferably prepared by applying one or more copolymers or compositions according to the present invention to a support and irradiating the copolymer or copolymer mixture with an alignment light after imidization or without imidization. The aligned light has the above-mentioned meaning and preference.

The term "support" as used in the context of the present invention is preferably a transparent or non-transparent, preferably glass or plastic substrate, a polymeric film such as polyethylene terephthalate coated with indium tin oxide (ITO) PET), tri-acetylcellulose (TAC), polypropylene, but are not limited thereto.

In general, the compositions comprising the copolymers of the present invention are applied by common coating and printing methods known in the art and include, for example, spin-coating, meniscus-coating, wire-coating, , Flexo-printing, gravure-printing, ink-jet printing may be used. Coating methods include, for example, spin coating, air doctor coating, blade coating, knife coating, reverse-roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, slot-orifice coating, , Electrodeposition coating, dip coating or die coating.

Which is a non-flexible or soluble substrate, optionally coated with indium tin oxide (ITO) or Pedot: PSS (poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate) Or a transparent support such as a plastic is used. The flexible substrate is used for a flexible LCD.

Printing methods include, for example, relief printing, such as flexographic printing, ink jet printing, intaglio printing, such as direct gravure printing or offset gravure printing, lithographic printing such as offset printing, or stencil printing, .

A more preferred embodiment of the present invention relates to an unstructured or structured oriented layer.

The present invention also relates to a process for the preparation of structured copolymer layers which comprises varying the orientation and / or tilt angle of the orientation in the copolymer layer. The direction of this orientation and / or the change of the tilt angle can be performed, for example, by controlling the direction of irradiation of the alignment light. By selectively irradiating a particular region of the polymer, copolymer or oligomer layer, it is understood that a very specific region of the layer can be oriented. In this way, a layer having a defined tilt angle can be provided.

The irradiation time depends on the output of the individual lamp, and can vary from a few seconds to several hours. However, the photo-reaction can also be carried out, for example, by irradiating the homogeneous layer with a filter that only passes radiation suitable for the reaction.

More preferred is a method for producing a copolymer layer; A method of making a planar multi-domain orientation of a copolymer layer; And / or a method of producing a copolymer layer having a tilt angle within the suggested meaning and preferences of the present invention.

A more preferred embodiment of the present invention relates to an orientation layer comprising at least one copolymer according to the invention.

In the context of the present invention, the orientation layer has the same meaning and preference as the copolymer layer which is an orientation layer, and is preferably a photo alignment layer.

In the context of the present invention, the orientation layer is used for plane orientation (in-plane switching) of the liquid crystal or for vertical orientation of the liquid crystal.

In a more preferred embodiment, the invention relates to an alignment layer according to the invention and to its use for plane orientation of liquid crystals.

In the context of the present invention, the phrase "orientation of liquid crystal" means that the liquid crystal has a tilt angle.

As used in the context of the present invention, the term tilt angle is the angle between the liquid crystal director and the surface of the orientation layer. The liquid crystal director means the average direction of the long axis of the liquid crystal molecules. In the context of the present invention, planar orientation means that the tilt angle is less than 30 degrees, preferably 0 to 30 degrees.

In a preferred embodiment, the tilt angle of the liquid crystal induced by the photo-alignment layer is less than 10, preferably 0 to 10. In a more preferred embodiment, the tilt angle is less than 5, preferably 0 to 5, and in a most preferred embodiment the tilt angle is less than 1, preferably 0 to 1, more preferably 0 To 0.5 degrees. A tilt angle of less than 0.2 DEG or less than 0.1 DEG is preferable.

In the context of the present invention, the vertical orientation is such that the tilt angle is greater than 70, greater than 75, preferably greater than 80, greater than 85, more preferably 85 to 90, 87 DEG or 87 DEG to 88 DEG or 88 DEG to 89 DEG or 89 DEG to 90 DEG.

A fifth embodiment of the present invention is the use of said orientation layer for orientation, particularly planar orientation, of the following composition:

-a) a liquid crystal composition comprising at least one liquid crystal polymer or oligomer comprising at least one polymerizable liquid crystal monomer or a polymerized form of said polymerizable liquid crystal monomer, and / or

-b) a liquid crystal composition comprising at least one liquid crystal polymer or oligomer comprising at least one polymerizable liquid crystal monomer or a polymerized form of said polymerizable liquid crystal monomer, said liquid crystal composition being sandwiched between a pair of said alignment layers .

An example of a liquid crystal polymer (LCP) is described in US 2012/114907 A1, which is incorporated herein by reference.

LCP material as used in the context of the present application means a liquid crystal material comprising a liquid crystal monomer and / or a liquid crystal dimer and / or a liquid crystal polymer and / or a crosslinked liquid crystal. When the liquid crystal material comprises a liquid crystal monomer, such monomers may be polymerized after anisotropy is generated in the LCP material, typically due to contact with the photo-orienting material. The polymerization may be initiated by thermal treatment, or preferably by exposure to actinic light comprising UV-light. The LCP-material may consist of a single type of liquid crystal compound, but may also be a composition of different polymerizable and / or non-polymerizable compounds, wherein all the compounds need not be liquid crystalline compounds. In addition, the LCP material may contain additives, for example photo-initiators or isotropic or anisotropic fluorescent and / or non-fluorescent dyes.

Further, the present invention is preferably applicable to a liquid crystal display device, particularly a liquid crystal display device for inducing the planar orientation of an adjacent liquid crystal layer, in particular a cell provided with a planar orientation, for example, an IPS mode such as an IPS mode such as S- (IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II, e-IPS, , An alignment layer according to the present invention for operating PS-IPS (Polymer Stabilization IPS), Field Induced Light-Reactive Alignment IPS, FFS (Fringe Field Switching), TN (Twisted Nematic), STN (Super Twisted Nematic) .

The liquid crystal composition of the present invention comprises a polymerizable monomer or a polymer or oligomer in a polymerized form of the polymerizable monomer. The polymerizable monomer or polymer or oligomer is bifunctional and / or has a rigid core (e.g., benzene). More preferred are polymeric monomers, or polymers or oligomers, having at least one ring or condensed ring structure and a functional group directly bonded to the ring or condensed ring structure.

More preferred liquid crystals have monomers of formula (VIII): < RTI ID = 0.0 >

[Wherein,

P ₁ and P ₂ are functional groups, and include acrylate, methacrylate, halogen acrylate such as fluoroacrylate, chloroacrylate; Oxetanyl, malanimidyl, allyl, allyloxy, vinyl, vinyloxy and epoxy groups,

S _a and S _b are independently of each other a single bond or a spacer unit which is preferably a linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more, preferably non-adjacent, The C-atom, CH- or CH ₂ - group may be replaced by a linking group within the meanings and preferences given above, preferably a single bond, -O-, -O (CO), -S-, - or

, -NR ¹² -, wherein the substituent is preferably one or more C ₁ -C ₆ alkyl, preferably methyl, R ¹² is lower alkyl,

Ab ₁ and Ab ₂ are cyclic structures and are independently selected from unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic groups having the meanings and preferences given in the present invention, Phenylene, naphthalene-2,6-diyl, terphenyl, quaterphenyl, phenanthrene group,

Zb ₁ represents -O-, -CO-, -CH (OH) -, -CH ₂ (CO) -, -OCH ₂ -, -CH ₂ O-, -O-CH ₂ -O-, -OCO-, - (CO) - ( CO) -, -OCF 2 -, -CF 2 O-, -CF 2 -, -CON (C 1 -C 16 _{alkyl) -, - (C 1 -C} 16 alkyl ) -NCO-, -CONH-, -NHCO-, -HNOCO-, -OCONH-, -NHCONH-, -OCO-, -CO-S-, -S-CO-, -CSS, -SOO-, -SO-, -SO-, -CH ₂ (SO) -, -SO ₂ -, -CH = CH-, -C≡C-, -CH = CH-COO-, -OCO- _{-CH = N-, -C (CH 3} ) = N-, -N = N- or a single bond; Or cyclic, straight-chain or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more C-atoms, CH- or CH ₂ -groups may be replaced independently of each other by a linking group;

Preferably, ₁ Zb is -O-, -CO-, -COO-, -OCO-, -OCOO-, -OCF 2 -, -CF 2 O-, -CON (CH 3) -, - (CH 3 ) -NCO-, -CONH-, -NHCO-, -CO-S-, -S-CO-, -CSS, -SOO-, -OSO-, -CSS-, -SOO-, -OSO-, -CH ₂ (SO ₂ ) -, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH═CH-, -C≡C-, -CH═CH-COO-, -OCO- CH- or a single bond;

More preferably, Zb ₁ is -COO-, -OCO-, -OCOO-, -OCF ₂ -, -CF ₂ O-, -CON (CH ₃ ) -, - (CH ₃ ) NCO-, -CONH- -CO-S-, -S-CO-, -CS-S-, -SOO-, -OSO, in particular -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, _{-CON (CH 3) -, -} (CH 3) NCO-, -CONH-, -NHCO- , or a single bond;

Most preferably, ₁ Zb is a single bond, -COO- or -OCO-, and;

and g is an integer of 1, 2 or 3.

In the formula (VI), P ₁ and P ₂ are preferably acrylate or methacrylate groups, S _a and S _b are single bonds, Zb ₁ is preferably a single bond, g is preferably 0 or 1.

Most preferably, the liquid crystal is a compound represented by any one of formulas (IX), (X), (Xa), (XI) or (XIb)

[Wherein,

P ₁ and P ₂ are independently from each other an acrylate, methacrylate, oxetane, maleinimide, allyl, allyloxy, vinyl, vinylamide, vinyloxy and epoxy groups, epoxy derivatives, butoxy and butoxy derivatives,

B is a single bond, -CO-C (C ₁ -C ₆ alkoxy) ₂ -, -COO-, -OCO-,

Of the liquid crystal _{Y 1, Y 2, Y 3} , Y 4, Y 5, Y 6 , independently of each other hydrogen, or unsubstituted or fluorine-substituted straight-chain or branched C ₁ -C ₁₆ alkyl group, di - (C ₁ - C ₁₆ alkyl) amino, C ₁ -C ₁₅ alkyloxy, nitro, nitrile and / or chlorine; Wherein one or more C-atoms, CH- or CH ₂ -groups are, independently of each other, a linking group; Halogen or nitrile; Preferred substituents are C ₁ -C ₆ alkyl groups, especially methyl or ethyl, C ₁ -C ₆ alkoxy groups, especially methoxy or ethoxy, chlorine, fluorine or nitrile, more preferably methoxy, chlorine, fluorine, or CN And most preferably methoxy, chlorine or fluorine; Also, when an aromatic group is substituted, it is preferably mono- or di-substituted;

S ₁ and S ₂ of the liquid crystal are spacer units that are independently of each other a single bond, or preferably a linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more, preferably non- The adjacent, C-atom, CH- or CH ₂ - group may be replaced by a linking group within the meanings and preferences given above, preferably a single bond, -O-, -O (CO), -S-, - ) O- or

, -NR ¹² -, wherein the substituents are preferably one or more C ₁ -C ₆ alkyl, preferably methyl, and R ¹² is lower.

In formula (IX), P ₁ and P ₂ are preferably acrylate or methacrylate groups, S ₁ and S ₂ are single bonds, Z ₁ is preferably a single bond, and n is preferably 0 or 1.

In the formulas (IX) and (XI), the substituent group for the benzene ring is present at the o-, m- or p-position. In the formula (X), the group of substituents for the naphthalene ring may be selected from the group consisting of o-, m-, p-, ana-, E-, kata- ) -Position, pros-position, amphi-position, or 2,7-position. The substituent group of the benzene ring is preferably in the p-position in the above position. Substituent groups for the naphthalene ring are preferably present in the amphipatic position in the above positions.

Preferred are:

In general, the liquid crystal composition or the liquid crystal layer is not particularly limited as long as they contain the mono- and / or multi-polymerizable monomers described above. Accordingly, the liquid crystal composition or the liquid crystal layer can be produced by any of a variety of publicly known liquid crystal materials. The liquid crystal composition or the liquid crystal layer may be the same or different liquid crystal material as the liquid crystal material for display.

In a sixth embodiment, the present invention relates to a method of manufacturing a liquid crystal display.

In the context of the present invention, the term "display" has the same meaning as the term "panel ".

The manufacturing method of the liquid crystal display panel may include using a polymerization initiator such as methyl ethyl ketone peroxide and a benzoyl ether compound.

Preferably, the present invention relates to a composition comprising at least a single LCP on a layer of siloxane polymer, copolymer or oligomer according to the first or second embodiment of the present invention, or preferably on the alignment layer according to the fourth embodiment of the present invention And polymerizing the LCP. BACKGROUND OF THE INVENTION

In general, the polymerization of LCP is carried out by irradiation or at elevated temperatures.

The LCP can be applied in an arbitrary amount on the orientation layer, and therefore the amount thereof is not particularly limited. The amount can be appropriately set according to the thickness of each of the LCP polymer films formed by, for example, polymerization of the monomer LCP.

The present invention also relates to a liquid crystal composition comprising a polymerizable liquid crystal monomer as described above or a polymer or oligomer in a polymerized form of the polymerizable liquid crystal monomer at least in a single orientation layer according to the invention, And then polymerizing the polymerizable liquid crystal monomer. The present invention also provides a method for producing a liquid crystal display comprising the steps of:

Generally, polymerization methods are not limited unless they adversely affect the apparatus from which they are made. Preferably, the polymerization is carried out by irradiation, in particular UV irradiation, or by heat.

More specifically, a method of manufacturing a liquid crystal display comprising an orientation layer and an electrode according to the present invention, preferably an LCD comprising a planar orientation of liquid crystals, more particularly an IPS mode, Wherein the exposure induces an orientation direction of the liquid crystal perpendicular to the polarized light, and / or the exposure, and preferably the first exposure, is directed to the alignment direction of the liquid crystal , And / or the exposure to polarized light, preferably the first exposure, is performed at an angle > 70 DEG between the electrode and the direction of the polarized light .

A seventh object of the present invention relates to an optical or electro-optical unstructured or structured element comprising a copolymer according to the invention or an orientation layer according to the invention.

In a preferred embodiment, the element is a liquid crystal display cell.

In the context of the present invention, elements, devices, cells, structures all refer to objects comprising polymerized or polymeric liquid crystals oriented by the copolymers according to the present invention.

Preferably, the invention also relates to an unstructured or structured element optical or electro-optical device, in particular an LCD, comprising a pair of opposing substrates; The substrate is provided with a pair of alignment layers according to the invention and the following:

- a) optionally, an LCP polymer film, said polymer film being formed on an orientation layer, or

- b) a liquid crystal composition comprising a polymer, preferably made of at least a polymerizable liquid crystal monomer, said liquid crystal composition being sandwiched between a pair of alignment layers.

The present invention also relates to the use of such an orientation layer for the orientation of liquid crystals, preferably for planar orientation, preferably in the production of unstructured or structured optical- or electro-optical elements, preferably in the production of hybrid layer elements will be. Preferably, these optical or electro-optical devices have at least one orientation layer, as well as unstructured and structured optical elements and multilayer systems. The layer or each layer may contain one or more regions of different spatial orientation.

The direction of the polarized light means the intersection of the orientation layer surface and the polarization plane of the polarized light during exposure. When polarized light is polarized in an elliptical shape, the polarization plane means a plane defined by the incident direction of light and the principal axis of the polarization ellipse.

The term polarized light direction is used in the context of the present invention not only to describe the orientation during the period of the exposure process but also to refer to the direction of the polarized light on the orientation layer as applied during exposure after exposure.

The electrodes are preferably in the form of parallel stripes, jig-zag or comb-like electrodes.

Preferably, the present invention relates to optical and electro-optically unstructured or structured components, preferably liquid crystal display cells, multilayer and hybrid layer elements comprising one or more polymer layers, copolymers or oligomer layers according to the invention will be.

The phrase optical or electro-optical elements of the present invention are preferably used as a display waveguide, a security or brand protection element, a bar code, an optical grating, a filter, a retarder, a compensation film, a reflective polarizing film, an absorbing polarizing film, A twisted retarder film, a cholesteric liquid crystal film, a guest-host liquid crystal film, a monomer wrinkle film, a smectic liquid crystal film, a polarizer, a piezoelectric cell, a thin film exhibiting non-linear optical characteristics, ornamental Optical components, brightness enhancement films, components for wavelength-band-selective compensation, components for multi-domain compensation, components for multi-view liquid crystal displays, non-dye retarders, polarization correction / Components of a sensor, components of a luminance enhancement film, components for a light-based communication device, G / H-polarizers with an anisotropic absorber, reflection (TN) liquid crystal display, a hybrid aligned nematic (HAN) liquid crystal display, an electronically controlled birefringent (ECB) liquid crystal display, a super twisted nematic (STN) liquid crystal displays, optically compensated birefringent (OCB) liquid crystal displays, pi-cell liquid crystal displays, PLS technology (planar two line switching), PS-IPS (Super IPS), AS-IPS (Advanced Super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II , e-IPS, p-IPS (high performance IPS); Field induced light-reactive orientation IPS, fringe field switching (FFS) liquid crystal display; (FPA) field induced light-reactive orientation; Hybrid FPA; VA-IPS mode liquid crystal display, or a multi-layer system or apparatus for the manufacture of a display using a blue liquid crystal; All such display types are applied in a transmissive or reflective or transflective mode.

More preferred optical or electro-optical elements include, but are not limited to, PLS technology (planar two line switching), PS-IPS (Polymer Stabilization IPS), Inplane Switching IPS), AS-IPS (Advanced Super IPS), E-IPS (Enhanced IPS), H-IPS (Horizontal IPS), UH-IPS, S-IPS II, e-IPS, p-IPS (High Performance IPS); Field induced light-reactive orientation IPS, fringe field switching (FFS) liquid crystal display; (FPA) field induced light-reactive orientation; Hybrid FPA; A VA-IPS mode liquid crystal display, or a display using a blue liquid crystal; All such display types are applied in a transmissive or reflective or transflective mode.

The advantages of the present invention have not been anticipated by those skilled in the art.

Surprisingly, the copolymers of the present invention have been found to orient polymerized or polymerizable liquid crystals upon irradiation of polarized light. In addition, the photo-orienting material exhibits good and uniform planar orientation quality and good electro-optical quality, for example good voltage retention or good image sticking characteristics, especially at high annealing temperatures. Additional embodiments will demonstrate that the inventive copolymers have good or very good afterimage characteristics, contrast ratio and voltage holding ratio.

Additional embodiments are non-limiting examples of embodiments that further illustrate the present invention.

Example

Definitions used in the Examples:

^& Lt; ¹ > H NMR: ¹ H nuclear magnetic resonance spectroscopy

DMSO-d ₆ : Deuterated dimethylsulfoxide

300 MHz: 300 MHz

M: Multiply term

D: Double term

Dd: double doublet

t: triplet

s: Sunshine

q: quadrant

qi:

br: Wide peak

HCl: hydrogen chloride

HCl solution (25%): volume%

NaOH: Sodium hydroxide

NaOH (30%): wt%

MeOH: methanol

EtOAc: ethyl acetate

NMP: N-methyl-2-pyrrolidone

THF: tetrahydrofuran

TBME: tert.-butyl methyl ether

DMF: N, N-dimethylformamide

DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene

NaHCO ₃ : Sodium bicarbonate

H ₂ SO ₄ : Sulfuric acid

RT: room temperature, typically in the range of 18 DEG C to 28 DEG C

[?]: viscosity

v.t.%: volume%

GPC: gel permeation chromatography. GPC is measured with a UV detector and polystyrene as a standard.

Mw: molecular weight

PI: polydispersity index

MLC7067: A mixture of liquid crystals commercially available from Merck KGA having a dielectric anisotropy of 10.3, an optical anisotropy of 0.1025 and a rotational viscosity of 81 mPa.s.

Example 1:

Preparation of 4- (3-cyanopropoxy) benzoic acid compound 1

46.8 g (307 mmol) of methyl-4-hydroxybenzoate, 50 g (338 mmol) of 4-bromobutanenitrile are dissolved in 535 mL of NMP. 5.1 g (31 mmol) of potassium iodide and 128 g (93 mmol) of potassium carbonate are added and the suspension is heated to 80 < 0 > C. After 48 h, a mixture of 15 g of sodium hydroxide and 49 ml of water is added. The reaction mixture is heated to 100 < 0 > C for 5 hours. The solution is then cooled and 480 mL of water is added. The aqueous layer is removed and the organic layer is poured into 1.5 L of ice water. Add 81 mL of 25% HCl solution. The precipitate is filtered off and washed with 250 mL of water. The resulting product is taken up in 600 mL of MeOH. The suspension was then stirred for 1 hour and filtered off to give 50.1 g (80%) of compound 1 as a white solid which was used without further purification.

Example 2:

(2E) -3- (4 - {[4- (3-nitrylpropoxy) benzoyl] oxy} phenyl) prop-

16.8 g (82 mmol) of Compound 1 are suspended in 56 mL of toluene and a few drops of DMF are added. The suspension is heated to 75 [deg.] C and 10.7 g (90 mmol) of thionyl chloride are added. After 2 hours, the excess thionyl chloride is removed under reduced pressure. Cool the solution to room temperature. 10.2 g (83 mmol) of 4-hydroxybenzaldehyde, 0.5 g (4 mmol) of 4-diaminopyridine and 28 g (355 mmol) of pyridine are added. After 3 hours, 14.5 g (140 mmol) of malonic acid and 3 g (42 mmol) of pyrrolidine are added. The reaction mixture is allowed to react at 80 占 폚 for 30 minutes. After incorporating 16.8 mL of MeOH, the suspension is cooled and maintained at 0 < 0 > C for 1 hour. The product is filtered off and suspended in a solution of 57 mL of MeOH, 11 mL of water and 7.5 g of 25% HCl solution for 2 hours. The solid is filtered off and washed with MeOH and heptane. Crystallization of the product in acetonitrile gives 23 g (80%) of compound 2 as a white solid.

Example 3:

Preparation of methyl 6- [4- (cyanomethyl) phenoxy] hexanoate Compound 3

5.65 g (42 mmol) of (4-hydroxyphenyl) acetonitrile and 9.1 g (44 mmol) of methyl 6-bromohexanoate are dissolved in 75 mL of N, N-dimethylformamide. 6.45 g (46 mmol) of potassium carbonate and 0.7 g (4 mmol) of potassium iodide are added and the suspension is heated to 80 < 0 > C. After 5 h, the mixture is cooled to 0 < 0 > C with an ice bath. 375 ml H ₂ O and 12.4 g HCl 37% are slowly added. Remove the precipitate was filtered, washed with 500 ㎖ of H ₂ O. The white solid is dried under vacuum at 40 < 0 > C overnight to give 11.2 g of 6- [4- (cyanomethyl) phenoxy] hexanoic acid.

Examples 3a, 3b, 3c and 3d:

Compounds 4, 5, 6 and 7 were prepared by reacting methyl 6-bromohexanoate with methyl 4-bromobutanoate, methyl 5-bromopentanoate, methyl 8-bromooctanoate, methyl 11- &Lt; RTI ID = 0.0 > 3-undecanoate < / RTI >

Example 4:

Preparation of methyl 6- (4-formylphenoxy) hexanoate compound 8

Compound 8 is prepared according to the method described for compound 3, except that (4-hydroxyphenyl) acetonitrile is replaced by 4-hydroxybenzaldehyde.

Examples 4a, 4b, 4c and 4d:

Compounds 9, 10, 11 and 12 were prepared by reacting methyl 6-bromohexanoate with methyl 4-bromobutanoate, methyl 5-bromopentanoate, methyl 8- bromooctanoate, methyl 11- &Lt; RTI ID = 0.0 > 8 < / RTI >

Example 5:

Preparation of 6- [4- (1-cyano-2-phenyl-vinyl) phenoxy] hexanoic acid compound 13

8.85 g (35 mmol) of compound 3, 3.8 g (35 mmol) of benzaldehyde are dissolved in 30 mL of propan-2-ol. The solution is heated to 60 < 0 > C and 1.77 mL (1.9 mmol) of a 2 M solution of tetrabutylammonium hydroxide in methanol is added dropwise. After 2 h at 60 < 0 > C, the reaction mixture is cooled to 0 < 0 > C. The precipitate is filtered off and washed with cold propan-2-ol. 7.4 g of the solid are dissolved in 55 ml of dimethylacetamide and then a solution of 1.35 g of NaOH and 1.2 g of H ₂ O in 55 ml of MeOH is added. When the reaction is complete, pour the reaction mixture slowly to a solution of 13.2 g of 25% HCl and 316 g of H ₂ O. The precipitate was filtered off and dried under vacuum to give 6.5 g of a white powder.

Examples 5a, 5b, 5k, 5l:

Compounds 14, 15, 23, and 24 are prepared according to the method described for compound 13, except that compound 3 is replaced with compound 5, compound 7, compound 6,

Examples 5c and 5d:

Compounds 17 and 18 are prepared according to the method described for compound 13, except that benzaldehyde is replaced with 4-fluorobenzaldehyde, 4-trifluoromethylbenzaldehyde, respectively.

Example 5e:

Compound 19 is prepared according to the method described for Compound 13, except that Compound 3 is replaced by Compound 8 and benzaldehyde is replaced by benzonitrile.

Examples 5f, 5j:

Compounds 20 and 25 are prepared according to the method described for compound 19, except that compound 8 is replaced with compound 12, compound 10, respectively.

Example 5g:

Compound 21 is prepared according to the method described for compound 19, except that compound 8 is replaced by compound 10 and benzaldehyde is replaced by 4-trifluoromethylbenzaldehyde.

Example 5h:

Compound 22 was prepared according to the method described for compound 21, except that 4-trifluoromethylbenzaldehyde was replaced with 2- (3,5-dimethoxyphenyl) acetonitrile.

Example 5i:

Compound 26 was prepared according to the method described for compound 21, but replacing 4-trifluoromethylbenzaldehyde with 4-fluorobenzaldehyde.

Example 6:

Preparation of Polymer P3

Compound 14 5.05 g (14 mmol) of compound 2 and 0.27 g (0.7 mmol) of suspended in 35 ㎖ of 4-methyl-2-pentanone, and 0.54 g H ₂ O a. 0.16 g (0.75 mmol) of tetraethylammonium bromide is added to give a white suspension. 4.25 g (14.2 mmol) of 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane are added dropwise. The mixture is stirred under reflux for 48 h. Cool the suspension. The upper liquid phase is removed and the polymer is rinsed with 25 ml of 4-methyl-2-pentanone. 20 mL of tetrahydrofuran and 50 mL of ethyl acetate are added, and the mixture is extracted with 15 mL of water. The resulting solution is slowly poured into 240 mL of cold tert-butyl methyl ether. The solid is filtered off and washed with 10 mL of tert-butyl methyl ether. The white solid obtained is dried under vacuum to give 5.45 g of polymer.

Mw (DA): 171120, Mn (DA): 75600, PI: 2.26

Example 7:

Preparation of polymer P2

Polymer P2 is prepared according to the method described for Polymer P1, except 5.05 g (14 mmol) of compound 2 and 0.162 g (0.56 mmol) of compound 14 are used.

Mw (DA): 56450, Mn (DA): 34780, PI: 1.62

Example 8:

Preparation of Polymer P1

Polymer P3 was prepared according to the procedure described for polymer P1 except that 5.05 g (14 mmol) of compound 2 and 0.216 g (0.42 mmol) of compound 14 were used.

Mw (DA): 40960, Mn (DA): 25866, PI: 1.58

Example 9:

Preparation of polymer P4

Polymer P4 was prepared according to the procedure described for Polymer P1 except that 5.05 g (14 mmol) of Compound 2 and 0.378 g (0.98 mmol) of Compound 14 were used.

Mw (DA): 95700, Mn (DA): 59550, PI: 1.6

Example 10:

Preparation of Polymer P5

Polymer P5 is prepared according to the method described for polymer P1 except that 5.05 g (14 mmol) of compound 2 and 0.486 g (1.26 mmol) of compound 14 are used.

Mw (DA): 74130, Mn (DA): 41580, PI: 1.78

Example 11:

Preparation of Polymer P6

Polymer P6 is prepared according to the method described for Polymer P1, with the exception that Compound 14 is replaced by Compound 15. [

Mw (DA): 98100, Mn (DA): 41400, PI: 2.37

Example 12:

Preparation of polymer P7

Polymer P7 is prepared according to the method described for polymer P2 except that compound 14 is replaced by compound 13.

Mw (DA): 63100, Mn (DA): 36600, PI: 1.72

Example 13:

Preparation of Polymer P8

Polymer P8 is prepared according to the method described for Polymer P3, except that compound 14 is replaced by compound 19.

Mw (DA): 86080, Mn (DA): 41030, PI: 2.1

Example 14:

Preparation of Polymer P9

Polymer P9 is prepared according to the method described for Polymer P1, with the exception that compound 14 is replaced by compound 20.

Mw (DA): 117320, Mn (DA): 65240, PI: 1.8

Example 15:

Preparation of polymer P10

Polymer P10 is prepared according to the method described for polymer P3, except that compound 14 is replaced by compound 17.

Mw (DA): 128800, Mn (DA): 54640, PI: 2.36

Example 16:

Preparation of Polymer P11

Polymer P11 is prepared according to the method described for polymer P2, except that compound 14 is replaced by compound 17.

Mw (DA): 40390, Mn (DA): 26650, PI: 1.52

Example 17:

Preparation of Polymer P12

Polymer P12 is prepared according to the method described for Polymer P3, except that compound 14 is replaced by compound 21.

Mw (DA): 81530, Mn (DA): 44500, PI: 1.83

Example 18:

Preparation of polymer P13

Polymer P13 is prepared according to the process described for polymer P3, except that compound 14 is replaced by compound 18.

Mw (DA): 77920, Mn (DA): 40320, PI: 1.93

Example 19:

Preparation of Polymer P14

Polymer P14 is prepared according to the method described for Polymer P3, with the exception that compound 14 is replaced by compound 22.

Mw (DA): 72780, Mn (DA): 40218, PI: 1.8

Preparation of Polymer P15

Polymer P15 is prepared according to the method described for polymer P1 except that compound 14 is replaced by compound 23.

Mw (DA): 124830, Mn (DA): 43000, PI: 2.9

Preparation of Polymer P16

Polymer P16 is prepared according to the method described for Polymer P3, except that compound 14 is replaced by compound 23.

Mw (DA): 131250, Mn (DA): 45950, PI: 2.85

Preparation of polymer P17

Polymer P17 is prepared according to the method described for polymer P1, except that compound 14 is replaced by compound 24.

Mw (DA): 104670, Mn (DA): 37800, PI: 2.8

Preparation of Polymer P18

Polymer P18 is prepared according to the method described for Polymer P3, except that compound 14 is replaced by compound 24.

Mw (DA): 123240, Mn (DA): 46560, PI: 2.7

Preparation of polymer P19

Polymer P18 is prepared according to the process described for Polymer P3, except that compound 14 is replaced by compound 25.

Mw (DA): 125500, Mn (DA): 49740, PI: 2.5

Preparation of Polymer P20

Polymer P20 is prepared according to the process described for polymer P3, except that compound 14 is replaced by compound 20.

Mw (DA): 88125, Mn (DA): 32830, PI: 2.7

Preparation of polymer P21

Polymer P21 is prepared according to the method described for polymer P4, except that compound 14 is replaced by compound 17.

Mw (DA): 90110, Mn (DA): 43400, PI: 2

Preparation of polymer P22

Polymer P22 is prepared according to the method described for Polymer P1, with the exception that compound 14 is replaced with compound 26.

Mw (DA): 87260, Mn (DA): 45360, PI: 1.9

Preparation of polymer P23

Polymer P23 is prepared according to the process described for polymer P3, except that compound 14 is replaced by compound 26. [

Mw (DA): 114970, Mn (DA): 48850, PI: 2.4

Example 20:

Comparative Example CP1:

49.2 g of Compound 2 are suspended in 375 ml of 4-methyl-2-pentanone and 5 g of water. 1.5 g of tetraethylammonium bromide is added to give a white suspension. 38.4 g of 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane is added dropwise. The mixture is stirred under reflux for 48 h. The suspension is cooled to room temperature. The upper liquid phase is removed and the polymer is rinsed with 150 mL of 4-methyl-2-pentanone. 140 mL of tetrahydrofuran are added and the mixture is heated to 50-60 DEG C with stirring until a (yellow) solution is obtained. The resulting yellow solution is slowly poured into a low temperature of 1.5 L in 10 min. The solid is filtered on a 15 cm Buchner with a paper filter (time: 2 min) and washed with 500 mL tert-butyl methyl ether. The white solid obtained (70.0 g) was dried under vacuum to give 70 g of polymer.

Mw (DA): 34500, Mn (DA): 22700, PI: 1.52

Example 21:

Production of PAA-1

0.666 g (3.4 mmol) of 1,2,3,4-cyclobutanetetracarboxylic acid are added to a solution of 0.69 g (3.47 mmol) 4- (4-aminophenoxy) aniline in 8.6 g NMP. Stirring is then carried out at 0 ° C for 2 hours. The polymer mixture is diluted with 50 mL of NMP, precipitated in 300 mL of water and dried at 40 [deg.] C under vacuum to obtain 2.1 g of polyamic acid PAA-1 in the form of a white powder.

[?] = 0.40 dL / g

Preparation of PAA-2

0.69 g (3.1 mmol) of 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride is added to a solution of 1.5 g (3.1 mmol) 4- (4-aminophenoxy ) &Lt; / RTI > aniline. Stirring is then carried out at 0 ° C for 2 hours. The polymer mixture is diluted with 30 g of NMP, precipitated in 300 mL of water and dried under vacuum at 40 DEG C, to obtain 1.9 g of polyamic acid PAA-2 in the form of a white powder.

[?] = 0.40 dL / g

Production of PAA-3

3.2 g (14.1 mmol) 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride was added to a solution of 3 g (14.1 mmol) 4,4'-ethylenedianiline Lt; / RTI > Stirring is then carried out at 0 ° C for 2 hours. The polymer mixture is then diluted with 47 g of acetone, precipitated in 500 mL of water and dried at 40 [deg.] C under vacuum, to obtain 6.5 g of polyamic acid PAA-3 in the form of a white powder.

[?] = 0.52 dL / g

Preparation of PAA-4

5.6 g (25.2 mmol) 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride was added to a solution of 5 g (25.2 mmol) 4,4'-methylenedianiline Lt; / RTI > Stirring is then carried out at 0 ° C for 2 hours. The mixture is then reacted at room temperature for 1 hour. The polymer mixture was then diluted with 100 g of NMP and 78 g of acetone and precipitated in 3500 mL of water and dried at 40 DEG C under vacuum to obtain 14 g of polyamic acid PAA-4 in the form of a white powder do.

[?] = 0.52 dL / g

Application example

Example 22 :

The liquid crystal is aligned by the photoreactive P1 and an electric field is applied between two planar electrodes on each side of the cell gap to produce a liquid crystal cell.

P1 and polyamic acid PAA-1 in a ratio of 10:90 per weight percent to form a blend composition in NMP, and the 6.3 wt% solution is prepared by thoroughly stirring until the solid is dissolved. A second solvent butyl cellosolve (BC) is then added and the entire composition is thoroughly stirred to give a final solution. The solvent ratio between NMP and butyl cellosolve is 1: 1. The polymer solution is spin-coated on two ITO coated glass substrates at a spin rate of 3600 rpm for 30 seconds. After spin coating, the substrate is subjected to a baking procedure consisting of pre-baking at 130 占 폚 for 1.5 minutes and post-baking at a temperature of 200 占 폚 for 40 minutes. The layer thickness obtained is about 90-110 nm. The substrate with the coated polymer layer on top is exposed to linearly polarized UV light (LPUV) at an angle of incidence of 0 [deg.] With respect to the normal to the substrate surface. The polarization plane is in a plane where the normal line of the substrate and the propagation direction of light are staggered. The applied dose is 100 mJ / cm2. After the LPUV exposure, the cell is assembled with two substrates, with the exposed polymer layer facing the interior of the cell. The substrates are adjusted with respect to each other such that the induced alignment directions are parallel to each other. The cell is a capillary filled with liquid crystal MLC7067 (Merck KGA) having a positive dielectric constant anisotropy. The cell is then optionally annealed at 130 DEG C for 30 minutes and cooled to room temperature. The cell is positioned between two crossed polarizers, the alignment quality of the liquid crystal in the cell is checked and adjusted to obtain a dark state. When the dark state does not show defects and the liquid crystal is sufficiently oriented, the orientation quality is defined as good. The orientation quality is defined as medium if the dark state has light leakage due to some non-uniform orientation of the liquid crystal in some area of the cell. When the liquid crystal is not aligned without darkness, the alignment quality is defined as poor.

The liquid crystal within the cell exhibits a well-defined and uniform planar orientation of the cell. Using a rotation analyzer method from Shintech, a tilt angle of less than 0.2 degrees is measured.

Example 22a :

The liquid crystal cell was prepared according to the method described for Example 22, except that the linearly polarized UV was used at an incident angle of 40 DEG to the normal of the substrate surface. The liquid crystal in the cell exhibits a sufficiently defined and uniform planar orientation before and after the thermal annealing of the cell. Using a rotation analyzer method from Shintech, a tilt angle of less than about 0.2 degrees is measured.

Example 23 :

The cell can be selected using the following methods: using P2, P3, P4, P5, P6, P7, P8, P9, P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20, P21, P22, , &Lt; / RTI > according to the method described for Example 22. The liquid crystals in all cells exhibit a sufficiently defined and uniform planar orientation after thermal annealing of the cell. Using a rotation analyzer method from Shintech, a tilt angle of less than 0.2 degrees is measured.

Example 24:

The after-images of the cells prepared in Examples 22 and 23 were measured. The after-image of the IPS cell is measured using Optipro-250 from Shintech. A wavelength of 589 nm is used. A non-deflected sample of two independent pixels is placed between the crossed polarizers and the orientation of the sample is made parallel to the first polarizer. The voltage-transmittance curve of the two pixels is obtained by applying a 60 Hz square wave voltage to find the voltage amplitude V ₁₀₀ for the maximum transmittance T ₁₀₀ and the voltage amplitude V ₁ (T ₁ [0]) reaching a transmittance of 1% . The second (reference, R) pixel remains in a non-biased state while a 60 Hz square wave voltage with amplitude V ₁₀₀ is applied to the first pixel (called the measurement pixel, M) for a period of 24 hours. During this time the sample is protected from light at room temperature and stored. After 24 hours, the transmittance T ₁ [24 h] is again measured for the two pixels using the same voltage V ₁ . The afterimage of the sample is as follows:

(24 h) = [TM 1 (24 h) / TM 1 (0 h)] × [TR 1 (0 h) / TR 1 (24 h)] × 100

(Where M denotes a measurement pixel and R denotes a reference pixel).

The residual image of the cell is considered to be very good (?) With a value of less than 109%, good (?) With a value of 109% to 113%, and poor () with a value of more than 113%.

As shown by Example 24, the after-image according to the copolymer according to the present invention is very good or good as compared with the after-image of Comparative Example CP1 which is poor.

Example 25 :

The orientation quality of the cells from Examples 22 and 23 is quantified by the contrast ratio (CR). The contrast of an un-deflected IPS cell can be measured by measuring its light leakage using a transmission microscope consisting of a backlight, a polarizer and an analyzer, an optical device (condenser lens, microscope objective) between the polarizers and a photomultiplier tube . As a light source, an LED backlight from ELDIM, similar to a backlight from a commercial display, is used. The area of measurement in the focal plane (sample) of the microscope objective is about 1 mm 2. Without the sample, the polarizer from the microscope moves to the vertical position (the detector signal indicates the minimum value). The un-biased sample is placed under the microscope objective, and the detector detects the minimum value V ₀ (The direction of cell alignment is parallel to the polarizer). By maintaining the in-plane position of the sample, the analyzer rotates 90 ° (until the detector displays the maximum value V _max ). The contrast of the sample is CR = V _max / V ₀ .

If the CR is less than 1000, the contrast is poor. If the CR is 1000 to 2000, the contrast is intermediate (●). If the CR is 2000 to 3000, the contrast is good (CR) CR is very good (

).

Example 26 :

The voltage holding ratio (VHR) of the cells from Examples 22 and 23 is measured at room temperature using an LCM-1 instrument from Toyo, Japan. The VHR is measured using a short frame period (T). The voltage attenuation V (at T = 20 ms) of the voltage surge of 64 μs at V ₀ (V at t = 0) = 5 V is measured over a period of T = 20 ms. Then, the voltage holding ratio provided by integration of the measurement curve between V ₀ and V, which is weighted by area in the case of 100% VHR, is determined at room temperature. The results show VHR ≥ 99% for all tested cells.

Claims

Copolymers comprising:
i. A first monomer having a side chain of formula (I):

[Wherein,
n ₀ is an integer from 0 to 4;
n ₁ is an integer from 0 to 15;
n ₂ is an integer from 0 to 15;
n ₃ is an integer from 1 to 15;
Each of X and Y independently represents H, F, Cl, CN;
S ₂ represents cyclic, aromatic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, wherein one or more -C-, -CH-, -CH ₂ - groups may be replaced by a linking group ;
E represents O, S, NH, C (C ₁ -C ₆ alkyl), NR ⁴ , OC, OOC, OCONH, OCONR ¹² , SCS, SC, wherein R ¹² is cyclic, Substituted or unsubstituted C ₁ -C ₂₄ alkyl, and one or more -C-, -CH-, -CH ₂ - group (s) may be substituted independently of each other by a linking group;
A represents a halogen or a substituted or unsubstituted C ₁ -C ₂₄ alkyl, a substituted or unsubstituted C ₁ -C ₂₄ alkenyl, a substituted or unsubstituted C ₁ -C ₂₄ alkynyl, or a carboxylic acid, One or more -C-, -CH-, -CH ₂ - groups may be replaced independently of each other by a heteroatom;
Z ₂ represents a chemical group having delignification of its electron density and / or inducing delocalization of the electron density of adjacent atoms thereof;
T represents a single bond, unsubstituted or substituted, straight-chain C ₁ -C ₁₆ alkyl;
* Indicates attachment to the polymer backbone; And
ii. A second monomer having a side chain of formula (II):

[Wherein,
n ₅ and n ₆ are independently of each other 0, 1 or 2;
E ₁ represents -O-, -CO-, -COO-, -OCO-, -NR ⁶ -, -NR ⁶ CO-, -CONR ⁶ -, -NR ⁶ COO-, -OCONR ⁶ -, -NR ⁶ CONR ⁶ -, -C = C-, -C = C-, -O-COO-;
S ₃ is a single bond, a spacer group selected from the group consisting of straight or branched C ₁ -C ₂₄ alkylene which is unsubstituted or substituted by cyano or halogen, wherein one or more CH ₂ groups are independently selected from the group consisting of hetero atoms, or -O-, -CO-, -COO-, -OCO-, -OOC-, -NR 6 -, -NR 6 CO-, -CONR 6 -, -NR 6 COO-, -OCONR 6 -, -NR ⁶ CONR ⁶ -, -C = C-, -C≡C-, -O-COO-;
Y ₁ and X ₁ independently of _one another are cyano or hydrogen;
Ar ₁ and Ar ₂ independently represent a ring system of 5 to 40 atoms, wherein each ring system is linked directly to a double bond of formula (II) via an electron conjugate (π-π bond) Or more unsaturation;
R ₁ , R ₂ , R ₃ and R ₄ are independently of each other hydrogen, C ₁ -C ₁₂ alkoxy, halogen, straight or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl, nitrile; or
R ₁ and R ₄ are hydrogen and R ₂ and R ₃ together form a residue of an electron-donating ring which is condensed to the Ar ₂ ring;
R ₅ , R ₆ and R ₇ are independently of each other hydrogen, C ₁ -C ₁₂ alkoxy, halogen, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl, nitrile or electron-donating single substituent; or
R ₅ and R ₆ together form a moiety of an electron-donating ring which is condensed to the Ar ₁ ring;
* Indicates attachment to the polymer backbone; And
Here, the polymer skeleton is a polysiloxane.

The copolymer according to claim 1, wherein the monomer of the polymer skeleton in the first monomer and the second monomer is represented by the formula (VI):

[Wherein,
R _a represents OH, Cl, a substituted or unsubstituted alkoxyl group having 1 to 20 carbons, an alkyl group having 1 to 20 carbons, or an aryl group having 1 to 20 carbons;
R ₀ represents OH, Cl, a linear or branched, substituted or unsubstituted alkoxyl group having 1 to 20 carbons, wherein -C-, -CH-, -CH ₂ - is unsubstituted or substituted C ₆ -C ₂₀ aryl group;
S ₁ is a single bond or a straight or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene, especially C ₁ -C ₁₂ alkylene, more particularly C ₁ -C ₈ alkylene, more especially C ₁ -C ₆ alkyl Most preferably C ₁ -C ₄ alkylene, most particularly C ₁ -C ₂ alkylene, wherein one or more of the -C-, -CH-, or CH ₂ - groups may be replaced by a linking group;
z is an integer from 0 to 15;
Z ₁ represents a single bond or a C ₃ to C ₁₂ substituted or unsubstituted aliphatic or alicyclic group;
* Denotes the attachment to the monomer of formula (I).

3. The method of claim 2,
R _a , R _o are as described above;
Z ₁ represents a substituted or unsubstituted C ₅ -C ₆ alicyclic group;
S ₁ represents substituted or unsubstituted C ₁ -C ₂₄ linear alkyl;
Copolymer.

The method according to claim 2 or 3,
R _a , R _o are as described above;
Z ₁ represents a substituted or unsubstituted cyclohexanol group or a substituted or unsubstituted cyclohexane ether group;
S ₁ represents an ethyl group
Copolymer.

2. The polymer of claim 1, wherein in the first monomer having a side chain of formula (I)
n ₀ , n ₁ , n ₂ , n ₃ , S ₂ , T are as described above;
A represents H, one or more halogens, one or more methoxy groups or one or more carboxyl groups;
E represents O, or S or NH;
X and Y are H;
Z ₂ is CN
Copolymer.

6. The composition of claim 5, wherein in the first monomer having a side chain of formula (I)
n ₀ , n ₁ , n ₂ , n ₃ , S ₂ , T, A, X, Y and Z ₂ are as described above;
E represents O
Copolymer.

The method of claim 1, wherein in the second monomer having a side chain of formula (II)
S ₃ , Ar ₁ , Ar ₂ , X ₁ , Y ₁ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , n ₅ and n ₆ are as defined above;
E ₁ is selected from the group consisting of -O-, -CO-, -COO-, -OCO-, -OOC-
Copolymer.

The method of claim 7, wherein in the second monomer having a side chain of formula (II)
S ₃ is unsubstituted straight or branched C ₁ -C ₂₄ alkylene wherein one or more CH ₂ groups may be substituted independently of one another by -O-,
Copolymer.

9. The method according to claim 7 or 8,
R ₁ , R ₂ , R ₃ and R ₄ independently of one another are hydrogen, C ₁ -C ₁₂ alkoxy, halogen, straight or branched, substituted or unsubstituted C ₁ -C ₂₄ alkyl, nitrile
Copolymer.

9. The method according to claim 7 or 8,
R ₁ and R ₄ are hydrogen;
R ₂ and R ₃ together, e is condensed to the Ar ₂ ring-forming residues of the donor and the ring; or
R ₁ , R ₂ , R ₃ and R ₄ are each independently of the other hydrogen, C ₁ -C ₁₂ alkoxy, halogen, straight or branched, halogen substituted or unsubstituted C ₁ -C ₂₄ alkyl,
Copolymer.

11. The method according to any one of claims 7 to 10,
R _5, R ₆ and R ₇ is hydrogen
Copolymer.

12. A composition comprising at least one first copolymer according to any one of claims 1 to 11, and a second polymer or copolymer not identical to the first copolymer, and optionally an additive.

An orientation layer comprising at least one copolymer according to any one of claims 1 to 11, or a composition according to claim 12.

Use of an orientation layer according to claim 13 for the alignment of liquid crystals.

An optical or electro-optic unstructured optical recording medium comprising at least one linear, branched or crosslinked copolymer according to any one of claims 1 to 11 or a composition according to claim 12 or an orientation layer according to claim 13. Or structuring elements, preferably liquid crystal display cells, multilayer and hybrid layer elements.