HK1239829B - Photoaligning material with lateral substitution - Google Patents

Description

Photo-aligned materials with lateral substitution

This application is a divisional application of the Chinese patent application with application number 201180008953.7, application date February 9, 2011, and invention name “Photo-aligned material with side substitution”.

Technical Field

The present invention relates to photoalignment materials with side substitution, compositions thereof, and their use in optical and optoelectronic devices, in particular liquid crystal devices (LCDs) or security devices.

Technical Background

In large-scale LCD manufacturing, the time intervals between different processing steps are very tightly controlled. In display manufacturing utilizing photoalignment technology, the UV exposure energy and its angle of incidence on the applied alignment layer are crucial and central to the process. This process step is optimized for a specific pretilt angle of the liquid crystal, along with the rest of the production process. Any desired change in pretilt angle typically requires time-consuming adjustments to the UV exposure unit. Consequently, more economical manufacturing processes are constantly sought after.

Summary of the Invention

In the present invention, new photo-alignment materials were discovered that enable desired pretilt angles to be obtained without significant changes to the production line.

A photo-alignment material comprising a polymer having at least one side-substituted portion represented by formula (I) on the side chain

in

A and B independently of one another represent an unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic group selected from a monocyclic ring of five or six atoms, two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, or a tricyclic ring system of thirteen or fourteen atoms;

Preferably, A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of five or six atoms, two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, or a tricyclic ring system of thirteen or fourteen atoms; and B represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic or alicyclic group selected from a monocyclic ring of five or six atoms, two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, or a tricyclic ring system of thirteen or fourteen atoms;

Z represents a bridging group,

R ¹ represents halogen, C ₁ -C ₁₆ alkoxy, C ₁ -C ₁₆ alkyl, nitro or nitrile, preferably methoxy, fluorine, chlorine or nitrile, and more preferably fluorine,

R ² and R ³ are independently of each other hydrogen, halogen or nitrile; unsubstituted or halogen-substituted C ₁ -C ₁₂ alkyl, wherein one or more C-atoms, CH- or CH ₂ -groups may be replaced by a linker; preferably R ² and R ³ are hydrogen, nitrile or fluorine, and more preferably R ² and R ³ are hydrogen and/or nitrile, and most preferably R ² and R ³ are hydrogen.

Substituents for aromatic or alicyclic groups are, for example, straight-chain or branched C ₁ -C ₁₆ alkyl groups (which are unsubstituted or substituted by fluorine, di(C ₁ -C ₁₆ alkyl)amino, C ₁ -C ₁₆ alkoxy, nitro, nitrile and/or chlorine; and wherein one or more C atoms, CH- or CH ₂ - groups may independently of one another be replaced by 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 nitrile, and most preferably methoxy, chlorine or fluorine. Furthermore, if the aromatic group is substituted, it is preferably substituted once or twice.

In the context of the present invention, halogen denotes fluorine, chlorine, bromine or iodine, and preferably fluorine or chlorine and more preferably fluorine.

In the context of the present invention, alkyl or alkylene is substituted or unsubstituted and has the same meaning for primary, secondary and tertiary alkyl or the corresponding alkylene; and wherein one or more C-atoms, CH- or _CH2- groups may independently of one another be replaced by a linking group.

Preferred _C1 - _C30 alkyl groups are especially _C1 - _C24 alkyl groups and preferably _C1 - _C16 alkyl groups, more preferably _C1 - _C12 alkyl groups, most preferably _C1 - _C6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, heneicosyl, docosyl, tricosyl or triacontanyl; more preferably _C1 - _C6 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl or hexyl.

Preferred di(C ₁ -C ₁₆ -alkyl)amino or C ₁ -C ₁₆ -alkoxy groups in the case of alkyl have the same preferences and meanings as given above.

In the context of the present invention, alkylene is substituted or unsubstituted and has the same meanings as primary, secondary and tertiary alkylene.

Preferred C ₁ -C ₂₄ alkylene groups are methylene, ethylene, propylene, isopropylene, butylene, sec-butylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene or hexadecanylene; more preferably C ₁ -C ₁₆ alkylene; most preferably C ₁ -C ₁₂ alkylene and particularly most preferably C ₁ -C ₆ alkylene.

The term "bridging group" as used in the context of the present invention is preferably selected from -O-, -CO-, _-CH (OH)-, -CH2(CO)-, _-OCH2- , _-CH2O- , -O-CH2-O-, -COO-, _-OCO- , -( _C1 - _C16alkylene )(CO)O-, -( _C1 - _C16alkylene )O(CO)-, -(CO)O( _C1 - _C16alkylene )-, -O(CO)( _C1 - _C16alkylene )-, -O(C1- _C16alkylene )-, -( _C1 - _C16alkylene )O-, _-OCF2- , _-CF2O- , -CON( _{C1 - C16alkylene} )-, -( _C1 -C16alkylene)- _C1- C24 alkylene) NCO-, -CONH-, -NHCO-, -HNOCO-, -OCONH-, -NHCONH-, -OCOO-, -CO-S-, -S-CO-, -CSS, -SOO-, -OSO-, -SOS-, -SO-, _-CH2 (SO)-, -SO2-, -CH=CH-, _-C≡C- , -CH=CH-COO-, -OCO-CH=CH-, -CH=N-, -C( _CH3 )=N-, -N=N- or a single bond; or cyclic, linear or branched, substituted or unsubstituted _C1 - _C24 alkylene, wherein one or more C-atoms, CH- or _CH2- groups may independently be replaced by a linking group.

Preferably, the bridging group is -O-, -CO-, -COO-, -OCO-, -OCOO-, _-OCF2- , _-CF2O- , -CON( _CH3 )-, -( _CH3 )NCO-, -CONH-, -NHCO-, -CO-S-, -S-CO-, -CS-S-SOO-, -OSO-, _-CH2 ( _SO2 )-, _-CH2-CH2- , _-OCH2- , _-CH2O- , -CH=CH-, -C≡C-, -CH=CH-COO-, -OCO _- CH=CH-, or a single bond.

More preferably, the bridging group is -COO-, -OCO-, -OCOO-, -OCF2-, _-CF2O- , -CON( _CH3 )-, -( _CH3 )NCO-, -CONH-, _-NHCO- , -CO-S-, -S-CO-, -CS-S-, -SOO-, -OSO, in particular -COO-, -OCO-, _-OCF2- , _-CF2O- , -CON( _CH3 )-, -( _CH3 )NCO-, -CONH-, -NHCO-.

The most preferred bridging groups are -COO-, -OCO-, -OCH ₂ -, -CH ₂ O- or a single bond, and in particular -OCO-, -OCH ₂ - or a single bond.

The term "linker" as used in the context of the present invention is preferably selected from a single bond, -S-, -S(CS)-, -(CS)S-, -CO-S-, -S-CO-, -O-, -CO, -CO-O-, -O-CO-, -NR ² -, -NR ² -CO-, -CO-NR ² -, -NR ² -CO-O-, -O-CO-NR ² -, -NR ² -CO-NR ² -, -CH=CH-, -C≡C-, -O-CO-O-, -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -; and unsubstituted or substituted cyclohexylene and unsubstituted or substituted phenylene and wherein:

^R2 represents hydrogen or _C1 - _C6 alkyl, in particular hydrogen or methyl, provided that the oxygen atoms of the linking group are not directly connected to each other; preferably a single bond, -O-, -O(CO), -S-, -(CO)O- or ^-NR2- ; more preferably a single bond, -O-, -O(CO) or -(CO)O-.

"Carbocyclic or heterocyclic aromatic radicals" and "aromatic groups" as used in the context of the present invention denote rings of 5, 6, 10 or 14 atoms, for example furan, benzene or phenylene, pyridine, triazine, pyrimidine, biphenylene, naphthylene, phenanthrene, benzo[9,10]phenanthrene, tetralin, which are uninterrupted or interrupted by at least a single heteroatom and/or at least a single bridging group; preferred "carbocyclic or heterocyclic aromatic radicals" and "aromatic groups" are benzene, phenylene, naphthylene, biphenylene, phenanthrene or benzo[9,10]phenanthrene, and more preferred are benzene, phenylene and biphenylene, in particular phenylene.

As used in the context of the present invention, the term "phenylene" preferably refers to 1,2-, 1,3- or 1,4-phenylene, which is optionally substituted. Preferably, the phenylene is 1,3- or 1,4-phenylene. 1,4-phenylene is particularly preferred.

The "alicyclic group" used in the context of the present invention denotes, for example, a ring system having 3 to 40 carbon atoms, preferably _C6 - _C40 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, decalin, tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroidal skeleton such as cholesterol, and preferably cyclohexane or a steroidal skeleton.

The term "polymer" used in the context of the present invention is not limited to and includes, for example, copolymers, polymers, homopolymers or oligomers, preferably homopolymers or copolymers.

The term "polymerization" as used in the context of the present invention is not limited to and includes, for example, copolymerization, polymerization, homopolymerization or oligomerization.

The photoalignment material used in the present invention comprises a polymer having a side chain and a main chain as described above, the main chain being not particularly limited and being represented by, for example, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polyurea, polyurethane, polystyrene derivative, poly(styrene-phenyl-maleimide)-derivative and poly(methyl)acrylate, cycloolefin polymer or a mixture thereof. Polyamic acid, polyimide, polyamic acid ester, polystyrene derivative and poly(styrene phenyl maleimide) derivative are preferred; polyamic acid ester, polyamic acid, polyimide and a mixture thereof are more preferred, and polyamic acid, polyimide and a mixture thereof are particularly preferred.

Furthermore, a photoalignment material is preferred, which comprises a polymer having at least one side-substituted moiety represented by the general formula (II) in a side chain, preferably in a mono- or polychromophoric side chain, in particular in a dichromophoric side chain.

in

B and Z have the meanings and preferences as described above,

R ¹ represents halogen, C ₁ -C ₁₆ alkoxy, C ₁ -C ₁₆ alkyl, nitro or nitrile, preferably methoxy, fluorine, chlorine or nitrile, and more preferably fluorine,

U represents hydrogen or linear or branched, unsubstituted or substituted at least once by halogen, nitrile, ether, ester, siloxane, amide or amine C ₁ -C ₁₆ alkyl, preferably substituted in the terminal position; in particular terminally substituted C ₁ -C ₁₂ alkyl, more particularly C ₁ -C ₆ alkyl, in which one or more C atoms, CH- or CH ₂ -radicals are independently of one another not replaced or replaced by a linker having the meanings and preferences given above; in particular C atoms, CH- or CH ₂ -radicals are replaced by -NH-, -NCH ₃ -, -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH-, -NH-CONH-, -NCH ₃ -, NCH ₃ -CO-, -CO-NCH ₃ -, -NCH ₃ -CO-O-, -O-CO-NCH ₃ -, -NCH ₃ -CONCH ₃ -, -O-, -CO, -CO-O-, -O-CO-, -CH=CH-, -C≡C-, -O-CO-O-, or substituted with unsubstituted or substituted cyclohexylene or phenylene;

Preferably, U is hydrogen or Q ¹ -(C ₁ -C ₁₆ alkyl), preferably Q ¹ -(C ₁ -C ₁₂ alkyl) and most preferably Q ¹ -(C ₁ -C ₆ alkyl), which is unsubstituted or substituted by halogen, nitrile, ether, ester, amide or amine; preferably substituted by fluorine or nitrile, in particular by 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, more in particular by 1, 2, 3, 4, 5, 6 or 7, and most in particular by 1, 2, 3 or 5 fluorine atoms; and wherein one or more C-atoms, CH- or CH ₂ -radicals of Q ¹ -(C ₁ -C ₁₆ alkyl) are independently unsubstituted or replaced by a linker having the meanings and preferences given above; in particular, a C-atom, CH- or CH ₂ -radical is replaced by -NH-, -NCH ₃ -, -NH-CO-, -CO-NH-, NH-CO-O-, -O-CO-NH-, -NH-CONH-, -NCH ₃ -, NCH ₃ -CO-, -CO-NCH 3 -, -NCH ₃ -CO-O-, -NCH _{3 -CO} -O-, -O-CO-NCH ₃ -, NCH ₃ -CONCH ₃ -, -O-, -CO, -CO-O-, -O-CO-, -CH=CH-, -C≡C-, -O-CO-O-, or unsubstituted or substituted cyclohexylene or phenylene; and wherein

Q ¹ represents a single bond or -NH-, -NCH ₃ -, -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH-, -NH-CONH-, -O-, -CO-, -COO-, -OCO-, -S-, -CS-, -SCS-, -SCO-, -CH=CH-, -C≡C-, or -O-CO-O-, preferably Q ¹ represents -O-, -CO-, -COO-, -OCO-, or a single bond, more preferably -O- or a single bond;

Preferably, the fluorine substituent of Q ¹ -(C ₁ -C ₆ alkyl) is at the terminal position of the alkyl group, on the side opposite to the attachment to B. More preferably, the substituted (C ₁ -C ₆ alkyl) is -CF ₃ , -CF ₂ H, -CH ₂ F, -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -CF ₂ CH ₂ F, -CFHCF ₃ , -CFHCHF ₂ , -CFHCH ₂ F, -CF ₂ CH ₃ , -CFHCHF ₂ , -(CF ₂ ) ₂ CF ₃ , -(CF ₂ ) ₂ CHF ₂ , -(CF ₂ ) ₂ CH ₂ F, -(CF ₂ ) ₂ CH ₃ , -(CF ₂ ) ₃ CHF ₂ , -(CF ₂ ) ₃ CH ₂ F, -(CF ₂ ) ₃ CF ₃ , -CF(CF ₃ ) ₂ or -CF ₂ (CHF) CF ₃ , and most preferably the formula -CF ₂ H, -CF ₂ H, -CH ₂ F, -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ ; and most preferably the formula -CF ₃ , -CH ₂ F, -CF ₂ CF ₃ , especially -CF ₃ ;

More preferably, U is hydrogen, _-CF3 , _-CF2H , _-CH2F , ^-Q1- (C1-C6 alkylene) _-CF3 , -Q1-( _C1 - _C6 alkylene)-CF2H, ^-Q1- ( _C1 - _{C6 alkylene)-CH2F, -Q1-(C1-C6 alkylene ) -CF2CF3 , -Q1-} ⁽ _C1 - _C6 alkylene)-CF2CHF2, ^-Q1- ( _C1 - _C6 alkylene) _-CF2CH2F , ^{-Q1- (} _C1 - _C6 alkylene) _-CFHCF3 , _{-Q1- ( C1} - ^{C6 alkylene)-CFHCHF2, -Q1-} ₍ ^{C1 -} _{C6 alkylene ) -CFHCH2F} , _-Q1- ( _{C1 - C6} alkylene ⁾ -CF ₁ -C ₆ alkylene)-CF ₂ CH ₃ , -Q ¹ -(C ₁ -C ₆ alkylene)-CFHCHF ₂ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₂ CF ₃ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₂ CHF ₂ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₂ CH ₂ F, -Q ¹ -(C ₁ -C ₆ alkylene)-(CF _{2 ) 2} CH ₃ , -Q ^{1 -} (C _{1 -C 6} alkylene)-(CF ₂ ) ₃ CHF ₂ , -Q ¹ -(C _{1 -C 6} alkylene)- _{( CF 2} ) ₃ CF ₃ , -Q ¹ -(C ₁ -C ₆ alkylene)-CF(CF ₃ ) ₂ , -Q ¹ -(C ₁ -C ₆ alkylene)-CF ₂ (CHF)CF ₃ ;

wherein one or more C-atoms, CH- or CH ₂ -radicals are independently of one another unsubstituted or replaced by a linking group having the meanings and preferences given above; in particular, a C-atom, CH- or CH ₂ -radical is replaced by -NH-, -NCH ₃ -, -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH-, -NH-CONH-, -NCH ₃ -, NCH ₃ -CO-, -CO _- NCH ₃ -, -NCH 3 -CO-O-, -O-CO-NCH ₃ -, -NCH ₃ -CONCH ₃ -, -O-, -CO, -CO-O-, -O-CO-, -CH=CH-, -C≡C-, -O-CO-O- or unsubstituted or substituted cyclohexylene or phenylene;

wherein -Q ¹ - has the meaning and preferred embodiment as described above,

R ² and R ³ independently of one another represent hydrogen, fluorine, chlorine, nitrile, unsubstituted or fluorine-substituted C ₁ -C ₁₂ -alkyl, where one or more C atoms, CH- or CH ₂ - groups may be replaced by a linker;

Preferably hydrogen, nitrile or F, and more preferably hydrogen;

X is a divalent aromatic group, such as phenylene, especially 1,4-phenylene; or X is _-CH2- , -CO-, -CS-, -O(CO)-, -(CO)O-, -NH(CO)-, -(CO)NH-, _-OCF2- , (( _C1 - _C6 alkyl)-N)CO-, preferably (( _CH3 )N)CO-, or -S(CS)-, -O(CS), -S(CO)-, preferably -O(CO)-.

More preferably, a photoalignment material comprises a polymer having at least one side substituent represented by formula (III) on a side chain, preferably on a mono- or poly-chromophoric side chain, in particular on a di-chromophoric side chain.

in

X, Z and U have the meanings and preferences as described above,

R ¹ represents halogen, C ₁ -C ₆ alkoxy, C ₁ -C ₁₆ alkyl, nitro or nitrile, preferably methoxy, chlorine, fluorine or nitrile and more preferably fluorine or methoxy;

R ^1′ and R ^1″ independently of one another represent hydrogen, fluorine, C ₁ -C ₆ alkoxy, nitrile and/or chlorine or U; preferably hydrogen, methoxy, fluorine or chlorine, and more preferably hydrogen or fluorine.

Furthermore, the present invention relates to compounds, in particular monomeric compounds, comprising at least one pendant substituted moiety and a polymerizable group, the pendant substituted moiety being represented by formula (I), preferably by formula (II) and more preferably by formula (III), as described above and with all preferences given above.

In the context of the present invention, the expression "polymerizable group" denotes an unsubstituted or substituted aliphatic, aromatic or alicyclic polymerizable group, wherein the "unsubstituted or substituted aliphatic" group is a _C1 - _C30 alkyl group, wherein one or more C-atoms, CH- or _CH2- groups may be replaced by a linking group; and wherein the "unsubstituted or substituted aromatic group" or "alicyclic group" has the meaning and preferences as described above.

In the context of the present invention, the phrase "polymerizable group" is not particularly limited and refers to preferably amine, diamine, acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenyl-acrylamide, N-(C ₁ -C ₆ ) alkyl-substituted acrylamide, N-(C ₁ -C ₆ ) alkyl-substituted methacrylamide, N-(C ₁ -C ₆ ) alkyl-substituted 2-chloroacrylamide, N-(C ₁ -C ₆ ) alkyl-substituted 2-phenylacrylamide, vinyl ether, vinyl ester, styrene, vinyl, carboxylic acid, carboxylic acid halide, carbonyl, siloxane, hydroxyl, halide, norbornene or mixtures thereof. Preferred polymerizable groups are amine, diamine, vinyl, acrylate or methacrylate, more preferably diamine groups, more preferably unsubstituted or substituted aliphatic, aromatic or alicyclic diamine groups, and most preferably aromatic diamine groups, including phenyl groups.

In particular, the most preferred is the compound represented by formula (IV)

in

B represents unsubstituted or substituted benzene, phenylene, pyridine, triazine, pyrimidine, biphenylene, naphthylene, phenanthrene, benzo[9,10]phenanthrene, tetralin, preferably phenylene, or an alicyclic group selected from cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, decalin, tetrahydrofuran, dioxane, pyrrolidine, piperidine and a steroid skeleton, preferably cyclohexane or a steroid skeleton; preferably B is benzene, phenylene, biphenylene or naphthalene, and more preferably B is unsubstituted or substituted phenylene;

R ¹ represents halogen, C ₁ -C ₁₆ alkoxy, C ₁ -C ₁₆ alkyl, nitro or nitrile, preferably methoxy, fluorine, chlorine or nitrile, and more preferably fluorine, chlorine or methoxy,

^R2 and ^R3 are hydrogen and/or nitrile, preferably hydrogen,

X is a divalent aromatic group, such as phenylene, especially 1,4-phenylene; or X is _-CH2- , -CO-, -CS-, -O(CO)-, -(CO)O-, -NH(CO)-, -(CO)NH-, _-OCF2- , (( _C1 - _C6 alkyl)-N)CO-, -( _C1 - _C16 alkylene)(CO)O-, -( _C1 - _C16 alkylene)O(CO)-, -(CO)O( _C1 - _C16 alkylene)-, -O(CO)( _C1 - _C16 alkylene)-, -O( _C1 - _C16 alkylene)-, -( _C1 - _C16 alkylene)O-, (( _CH3 )N)CO-, or -S(CS)-, -O(CS), -S(CO), preferably 1,4-phenylene, O(CS), -S(CO), -CS-, -CO- or -O(CO)-, and more preferably -CO- or -O(CO)- or 1,4-phenylene;

Z represents -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -(C ₁ -C ₁₆ alkylene)(CO)O-, -(C ₁ -C ₁₆ alkylene)O(CO)-, -(CO)O(C ₁ -C ₁₆ alkylene)-, -O(CO)(C ₁ -C ₁₆ alkylene)-, -O(C ₁ -C ₁₆ alkylene)-, -(C ₁ -C ₁₆ alkylene)O-, -CON(CH ₃ )-, -(CH ₃ )NCO-, -CONH-, -NHCO-, -OCH ₂ -, -CH ₂ O-, or a single bond, preferably -COO-, -OCO-, OCH ₂ -, -OCF ₂ -, -CF ₂ O-, -CH ₂ O-, or a single bond, in particular -OCO-, OCH ₂ -, or a single bond,

U is hydrogen, _-CF3 , _-CF2H , -CH2F, _-Q1- (C1- _{C6 alkylene)-CF3, -Q1-(C1-C6 alkylene} ⁾ _-CF2H , ^-Q1- (C1- _C6 alkylene) _-CH2F , ^-Q1- ( _C1 - _C6 alkylene) _-CF2CF3 , ^-Q1- ( _{C1 - C6} alkylene) _-CF2CHF2 , ^{-Q1- (} _C1 - _C6 alkylene) _-CF2CH2F , _-Q1- ( _C1 -C6 alkylene) _-CFHCF3 , _-Q1- ( _C1 - _C6 alkylene) _-CFHCHF2 ^{, -Q1-} ( _{C1 - C6} alkylene) _-CFHCH2F ^, _-Q1- ( ^C1 _{- C6} alkylene _{) -CF} -Q 1 -(C ₁ -C 6 alkylene)-CF ₂ CH ₃ , -Q ¹ -(C ₁ -C ₆ alkylene)-CFHCHF ₂ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₂ CF ₃ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₂ CHF ₂ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₂ CH ₂ F, -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₂ CH ₃ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₃ CHF ₂ , -Q ¹ -(C ₁ -C ₆ alkylene)-(CF ₂ ) ₃ CH ₂ F, -Q ¹ -(C ₁ -C ₆ alkylene)-(CF _{2 3} CF ₃ , -Q ¹ -(C ₁ -C ₆ alkylene)-CF(CF ₃ ) ₂ , -Q ¹ -(C ₁ -C ₆ alkylene)-CF ₂ (CHF)CF ₃ ; wherein one or more C-atoms, CH- or CH ₂ -radicals are independently unsubstituted or replaced by a linking group having the above-mentioned meanings and preferences; in particular, the C-atoms, CH- or CH ₂ -radicals are replaced by -NH-, -NCH ₃ -, -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH-, -NH-CONH-, -NCH ₃ -, NCH ₃ -CO-, -CO-NCH ₃ -, -NCH ₃ -CO-O-, -O-CO-NCH ₃ -, -NCH ₃ -CONCH ₃ -, -O-, -CO, -CO-O-, -O-CO-, -CH=CH-, -C≡C-, -O-CO-O-, or substituted by unsubstituted or substituted cyclohexylene or phenylene;

in

Q ¹ represents a single bond or -NH-, -NCH ₃ -, -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH-, -NH-CONH-, -O-, -CO-, -COO-, -OCO-, -S-, -CS-, -SCS-, -SCO-, -CH=CH-, -C≡C-, or -O-CO-O-, preferably Q ¹ represents -O-, -CO-, -COO-, -OCO-, or a single bond, more preferably -O- or a single bond;

D represents an unsubstituted or substituted aliphatic, aromatic or alicyclic polymerizable group, preferably a diamine group having 1 to 40 carbon atoms, more preferably D is an aromatic polymerizable group, most preferably an aromatic polymerizable diamine group; y and z are each independently of one another 1, 2, 3 or 4, preferably 1 or 2; more preferably y is 2 and z is 1; or z is 2 and y is 1; and further more preferably y and z are 1; w is 1, 2, 3, 4 and preferably 1 or 2, more preferably w is 1;

Furthermore, it is most preferred that w is 1, y is 2, and z is 1; and z is 2, and y is 1; or furthermore, it is most preferred that w is 1, y, and z are 1; particularly it is most preferred that w is 1, y is 2, and z is 1; and z is 2, and y is 1;

S ¹ and S ² each independently of one another represent a single bond or a spacer unit, which is a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ -alkylene group, preferably C ₁ -C ₁₂ -alkylene group, more preferably C ₁ -C ₆ -alkylene group, such as methylene, ethylene, linear or branched propylene, butylene, pentylene or hexylene group, wherein one or more, preferably non-adjacent C-atoms, CH- or CH ₂ -groups may be replaced by at least one linking group;

wherein the linking group is preferably a single bond, -O-, -O(CO), -S-, -(CO)O-, -C≡C-, or -NR ² -, and more preferably a single bond, -O-, -O(CO) or -(CO)O-, and most preferably -O-; and wherein the substituent of the C ₁ -C ₂₄ alkylene group is preferably at least one C ₁ -C ₆ alkyl group, preferably methyl; and/or a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (V):

-(Z ^1a' ) _a3' -(Z ¹ -C ¹ ) _a1 -(Z ² -C ² ) _a2 -(Z ^1a ) _a3 -(V)

in:

C ¹ and C ² each independently represent an alicyclic or aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, preferably C ¹ and C ² are linked via Z ¹ , Z ² , Z ^1a and/or Z ^1a ' at opposite positions so that the groups S ¹ and/or S ² have a long molecular axis, and

Z ¹ , Z ² , Z ^1a , and Z ^1a ′ each independently represent a bridging group having the above-mentioned meanings and preferences, and

a1, a3', a2, and a3 each independently represent an integer from 0 to 3, such that

a1+a3'+a2+a3≤6, preferably a3 and/or a3' is 1 and a1+a2≤4,

Most preferably, S ¹ and S ² each independently represent a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene group, preferably a C ₁ -C ₆ alkylene group, in particular a C ₁ -C ₂ alkylene group, further in particular a C ₄ -C ₁₂ alkylene group; and wherein one or more, preferably non-adjacent, C-atoms, CH- or CH ₂ -groups may be replaced by at least one linking group, wherein the linking group is preferably a single bond, -O-, -O(CO), -S-, -(CO)O-, -C≡C-, or -NR ² - and more preferably a single bond, -O-, -O(CO)- or -(CO)O- and most preferably -O-; in particular, most preferably, S ¹ and S ² together represent a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene group, preferably a C ₁ -C ₆ alkylene group, in particular a C ₁ -C ₂ alkylene group, further in particular a C ₄ -C ₁₂ alkylene groups.

More particularly, the most preferred compound is the compound of formula (IVa)

in

D represents an unsubstituted or substituted aliphatic, aromatic or alicyclic polymerizable group, preferably a diamine group having 1 to 40 carbon atoms, more preferably D is an aromatic polymerizable group, most preferably an aromatic polymerizable diamine group; w, y and z, as well as ^S1 , ^S2 and U have the above-mentioned meanings and preferred embodiments;

R is hydrogen or halogen, C ₁ -C ₁₆ alkoxy, C ₁ -C ₁₆ alkyl, nitro or nitrile, preferably methoxy, fluorine, chlorine or nitrile and more preferably fluorine, chlorine or methoxy,

R ^1′ , R ^1″ and R ^1″′ independently of one another represent hydrogen, methoxy, fluorine, nitrile and/or chlorine or U; provided that at least one of R ^1′ , R ^1″ or R ^1″′ is not hydrogen;

Preferably, R ^1' , R ^1" and R ^1"' are hydrogen and R is fluoro or methoxy;

Still more preferably R ^1″ and R ^1″′ are hydrogen and R is fluorine or chlorine and R ^1′ is fluorine or chlorine, or R ^1′ is fluorine and R is hydrogen; or

Still more preferably R ^1″ and R ^1′ are hydrogen and R and R ^1′″ are fluorine;

Z represents a bridging group having the above meanings and preferences; in particular, most preferred are compounds of formula (IVa), wherein if y, z and w are 1 and S ¹ represents butylene, pentylene or hexylene and S ² has the same meanings and preferences as mentioned for the particularly preferred compounds of formula (IV).

In the context of the present invention, in a preferred embodiment,

D represents an unsubstituted or substituted aliphatic, aromatic or alicyclic diamine group having 1 to 40 carbon atoms, more preferably D is an aromatic polymerizable group; D is preferably selected from the formula (VI):

H(R ⁵ )N-(Sp ¹ ) _k1 -(X ⁴ ) _t1 -(Z ⁴ -C ⁴ ) _a4 -(Z ⁵ -C ⁵ ) _a5 -(X ⁵ ) _t2 -(Sp ² ) _k2 -N(R ⁴ )H(VI)

in:

R ⁴ and R ⁵ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group;

Sp ¹ and Sp ² each independently represent an unsubstituted or substituted linear or branched C ₁ -C ₂₄ alkylene group, wherein one or more -CH ₂ - groups may be replaced by a linking group independently of each other,

k1, k2 are each independently 0 or 1, preferably 0; and

X ⁴ and X ⁵ each independently represent -O-, -S-, -NH-, -N(CH ₃ )-, -CH(OH)-, -CO-, -CH 2 (CO)-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -OCO-, -OCO- _O- , -S-CO-, -CO-S-, -SOO-, -OSO-, -SOS-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH＝CH-, or -C≡C-, or a single bond, preferably a single bond; and

t1, t2 are each independently an integer having a value of 0 or 1; and

C ⁴ and C ⁵ each independently represent a non-aromatic, aromatic, substituted or unsubstituted carbocyclic or heterocyclic group, which may have a side chain T, preferably an unsubstituted or substituted phenylene group, and

^Z4 and ^Z5 independently represent a single bond or a substituted or unsubstituted straight-chain or branched _C1 - _C24 alkylene group, wherein one or more C-atoms, CH- or _CH2- groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups; and/or by heteroatoms and/or by -O-, -CO-, -COO-, -OCO-, -OCF2-, _-CF2O- , -CON( _CH3 )-, -( _{CH3 )} NCO-, -CONH-, -NHCO-, -CO-S-, -S-CO-, -CS-S-, _-SOO- , -OSO-, -CH2( _SO2 )-, _{-CH2- CH2-} , _-OCH2- , _-CH2O , -CH=CH-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-; preferably, Z ⁴ is a single bond and Z ⁵ represents an unsubstituted or substituted straight-chain or branched C ₁ -C ₁₄ alkylene, C ₁ -C ₆ alkylene, in which one or more, preferably non-adjacent, -C-atoms, CH- or CH ₂ -groups may be replaced by oxygen or nitrogen atoms, and/or one or more carbon-carbon single bonds may be replaced by a carbon-carbon double bond or a carbon-carbon triple bond; and

a4, a5 are independently 0, 1, 2 or 3, such that a4+a5≤4, preferably a4 and a5 are independently 0 or 1, and more preferably at least one of a4 or a5 is 1, and most preferably a4 and a5 are 1; and wherein

D is linked at least once to ^S2 and/or ^S1 of at least one spacer group; and/or linked via at least one ^{of Sp1} , ^Sp2 , ^C4 , ^C5 and/or ^Z4 , ^Z5 , and wherein at least one of ^k1 , ^k2 , ^a4 and ^a5 is not equal to zero.

More preferably, D is selected from formula (VI), wherein:

C ⁴ and C ⁵ are independently selected from the group G ² compounds, wherein the group G ² represents:

More preferably, G ² represents:

in

"—" represents the bond between C ⁴ and C ⁵ and the adjacent groups of the compound of formula (VI) as described above; and

L is hydrogen, -CH ₃ , -COCH ₃ , -OCH ₃ , nitro, nitrile, halogen, -CH ₂ ═CH-, -CH ₂ ═C(CH ₃ )-, -CH ₂ ^═CH- (CO)O-, -CH 2 ═CH-O-, -NR ⁵ R ₆ , -CH _{2 ═C} (CH ₃ )-(CO)O-, -CH ₂ ═C(CH ₃ )-O-, wherein:

R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ -C ₆ alkyl group;

T represents a substituted or unsubstituted straight-chain or branched C ₁ -C ₂₄ alkylene group, wherein one or more C-atoms, CH- or CH ₂ -groups may be replaced independently of one another by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, or heteroatoms, and/or by bridging groups, preferably T is hydrogen;

m is an integer from 0 to 2; preferably 1 or 0; and more preferably 0;

u1 is an integer from 0 to 4, preferably 0; provided that m+u1≤4; and

u2 is an integer from 0 to 3, preferably 0; provided that m+u2≤3; and

u3 is an integer from 0 to 2, preferably 0; provided that m+u3≤2.

The diamine group D of the present invention is particularly preferably selected from the following structures: substituted or unsubstituted o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, benzyldiamine, aminophenylene-Z ⁵ -phenyleneamino, wherein Z ⁵ has the same meaning and preference as described above; naphthalene diamine, benzidine, diaminofluorene, 3,4-diaminobenzoic acid, 3,4-diaminobenzyl alcohol dihydrochloride, 2,4-diaminobenzoic acid, L-(+)-threo-2-amino-1-(4-aminobenzyl)-1,3-propanediol, p-aminobenzoic acid, [3,5-3h]-4-amino-2-methoxybenzoic acid, L-(+)-threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol, 2,7-diaminofluorene, 4,4'-diamino Octafluorobiphenyl, 3,3'-diaminobenzidine, 2,7-diamino-9-fluorenone, 3,5,3',5'-tetrabromo-biphenyl-4,4'-diamine, 2,2'-dichloro[1,1'-biphenyl]-4,4'-diamine, 3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cycloheptan-6-one, dibenzo(1,2)dithione-3,8-diamine, 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, tetrabromomethylenediphenylamine, 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, benzidine-3,3'-dicarboxylic acid, 4,4'-diamino -1,1'-binaphthyl, 4,4'-diaminodiphenyl-3,3'-diglycolic acid, dihydroethidium bromide, o-dianisidine, 2,2'-dichloro-5,5'-dimethoxybenzidine, 3-methoxybenzidine, 3,3'-dichlorobenzidine (diphenyl-d6), 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-dichloro-benzidine-d6, tetramethylbenzidine, di(aminophenyl)alkylene, and

The diamine group D is a group further selected from the amino compounds listed below, which do not have two amino groups and are considered derivatives with at least one additional amino group:

Aniline, 4-amino-2,3,5,6-tetrafluorobenzoic acid, 4-amino-3,5-diiodobenzoic 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-aminophenylethylmethanol, 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, parastigmine, 4-Amino-5-chloro-2-methoxybenzoic acid, 4-(Hexafluoro-2-hydroxyisopropyl)aniline, piperazine-p-aminobenzoate, 4-Amino-3,5-dibromobenzoic acid, isonicotinate hydrazine, p-aminosalicylate, 4-Amino-3,5-diiodosalicylate Acid, 4-amino-2-methoxybenzoic acid, 2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindole-1,3-dione, 4-amino-2-nitrobenzoic acid, 2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropionic acid ethyl ester, 2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropionic acid ethyl ester, 2-(4-amino-3-methoxyphenyl)-3 , ethyl 3,3-trifluoro-2-hydroxypropionate, 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-methoxybenzoic acid, 3,3'-benzidine-5-sulfonic acid, or derivatives thereof, with the proviso that the listed compounds without two amino groups are regarded as derivatives having at least one additional amino group.

More particularly, D is more preferably o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, benzylenediamine, aminophenylene-Z ⁵ -phenyleneamino, wherein Z ⁵ has the same meaning and preference as described above.

The diamine groups D are commercially available or can be obtained by known methods. Secondary amino groups can be obtained, for example, by substitution reactions.

D is furthermore particularly preferably a compound selected from the following:

as well as

More particularly, it is more preferred

in

L, L ₁ , L ₂ and L ₃ are independently hydrogen, -CH ₃ , -COCH ₃ , -OCH ₃ , nitro, nitrile, halogen, CH ₂ ═CH-, CH ₂ ═C(CH ₃ )-, CH ₂ ═CH-(CO)O-, CH ₂ ═CH-O-, -NR ⁵ R ⁶ , CH ₂ ═C(CH ₃ )-(CO)O- or CH ₂ ═C(CH ₃ )-O-, preferably hydrogen,

T, T ₁ , T ₂ and T ₃ are independently a single bond or a substituted or unsubstituted straight-chain or branched C ₁ -C ₂₄ alkylene group, wherein one or more C-atoms, CH- or CH ₂ -groups may be independently replaced by non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic groups, and/or heteroatoms and/or replaced by a linking group;

"—" is a single bond,

q is an integer of 1 or 2; and

q1, q2 and q3 are independently an integer from 0 to 2; preferably 1 or 2;

m is an integer of 1 or 2;

m1, m2 and m3 are independently an integer from 0 to 2; preferably 1 or 2;

u3, u3' and u3" are independently integers from 0 to 2;

R ⁵ , R ⁶ and Z ⁵ are as described above; preferably Z ⁵ is unsubstituted or substituted linear or branched C ₁ -C ₁₄ alkylene, C ₁ -C ₆ alkylene, wherein one or more, preferably non-adjacent, -C-atoms, CH- or CH ₂ -groups may be replaced by oxygen or nitrogen atoms; more preferably Z ⁵ is methylene, ethylene, propylene, 2,2-dimethyl-propylene, butylene, pentylene, hexylene, ₂ (-OC ₁ -C ₆ alkylene) methylene or ₂ (-(CO)OC ₁ -C ₆ alkylene) methylene or a monovalent or divalent group thereof; provided that,

D is connected to at least one of the groups ^S1 or ^S2 at least once through a single bond "-", or through a side chain T, _T1 , _T2 or _T3 , or through a group ^Z5

The condition is,

u3+q, or u3+m≤4;

u3+q1 or/and u3'+q2 or/and u3+m1, or/and u3'+m2, or/and u3"+q3, or/and u3"+m3≤4;

q1+q2, and ml+m2; and q1+q2+q3, and ml+m2+m3≥1.

Most preferably, the diamine compound according to the present invention is one in which D is selected from the following compounds:

More preferably

"—" indicates the connection of D to ^S1 or ^S2 and represents a single bond; and

L is _-CH3 , _-COCH3 , _-OCH3 , nitro, nitrile, halogen, _CH2 =CH-, _CH2 =C( _CH3 )-, _CH2 =CH-(CO)O-, _CH2 =CH-O-, ^-NR5R6 , _CH2 =C( _CH3 )-(CO)O- or _CH2 =C ⁽ _CH3 )-O-,

in:

R ⁵ and R ⁶ each independently represent hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen; u3 is an integer of 0-2, preferably 0.

Furthermore, it is preferred that the diamine groups D according to the invention are diamines of the following formulae (VII) to (XV):

H ₂ N-alkylene-NH ₂ (VII)

wherein the alkylene group is preferably a C ₁ -C ₂₄ alkylene group, which is connected at least once to X or S ¹ or S ² in the compound of formula (IV),

wherein the cyclohexylene group is connected at least once to X, ^S1 or ^S2 in the compound of formula (IV),

wherein X ⁴ or/and cyclohexylene is connected at least once to X or S ¹ or S ² in the compound of formula (IV),

wherein X ⁵ or/and phenylene is connected at least once to X or S ¹ or S ² in the compound of formula (IV), wherein X ⁵ is a C ₁ -C ₃₀ alkyl group,

wherein X ⁶ or/and phenylene is connected at least once to X or S ¹ or S ² in the compound of formula (IV),

wherein X ⁷ , X ⁸ or/and phenylene are connected at least once to X or S ¹ or S ² in the compound of formula (IV),

wherein X ⁹ , X ¹⁰ , X ¹¹ or/and phenylene are connected at least once to X or S ¹ or S ² in the compound of formula (IV), and

wherein X ⁴ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ and X ¹¹ are each independently a bridging group or a single bond; or a diamine of formula (XIV) selected from the compounds given below:

wherein X ⁵ has the above meaning and X ¹⁷ is CH ₂ , O, NH; and they are connected to X or S ¹ or S ² in the compounds of formula (IV) and (XV) on the aryl group

in

R ⁹ , R ¹⁰ , R ¹¹ independently have the above meanings, and R ⁹ and R ¹⁰ are C ₁ -C ₃₀ alkyl, preferably methyl and R ¹¹ is 2-methylheptane and if y is 1 then n is 0, and if n is 1 then y is 0, and y1 is a single bond or a double bond, and X ¹⁸ is a carbonyl group or a single bond or NH,

wherein X ¹⁷ is CH ₂ , O, or NH, and is connected to X or S ¹ or S ² in the compound of formula (IV).

The term "alkylene" as used in D represents ( _C1 - _C24 )alkylene, preferably ( _C1 - _C12 )alkylene, which is branched, linear, substituted, unsubstituted, uninterrupted or interrupted by the above-mentioned linking groups, and alicyclic groups, such as cyclohexylene or _C17 - _C40 alicyclic groups, having the meanings and preferences as described above; or -Si( ^R3 ) _2- or -O-Si( ^R3 ) _2- , wherein ^R3 represents hydrogen, fluorine, chlorine, nitrile, unsubstituted or fluorine-substituted _C1 - _C12alkyl , wherein one or more C-atoms, CH- or _CH2- groups may be replaced by a linking group; preferably hydrogen, methyl or fluorine, and more preferably hydrogen.

Furthermore, preferred in the present invention are diamine groups D(XV) in which X ¹² is a substituted or unsubstituted aliphatic or alicyclic group, preferably

wherein R ³ has the same meaning and preference as described above, and a, b and c are independently 1, 2 or 3, and c is an integer from 1 to 20; such as

wherein X ¹³ is methylene, ethylene, propylene or butylene, and R ³ has the same meaning and is preferably methyl, ethyl or propyl.

Further preferred are diamine groups D(VIII) of formula (VIII-1)

wherein ^R9 and ^R10 are independently of one another hydrogen, halogen, hydroxyl, a carbocyclic or heterocyclic non-aromatic group or a _C1 - _C30 alkyl group, which is branched, linear, substituted, unsubstituted, uninterrupted or interrupted as described above and preferably interrupted by a linker, and more preferably interrupted by a carbocyclic or heterocyclic non-aromatic group, such as a cyclohexylene or a _C17 - _C40 alicyclic group, and wherein the cyclohexyl group is connected to X or ^S1 or ^S2 in the compound of formula (IV).

Furthermore, preference is given to diamine groups D(IX-1)

in

X ¹⁴ is a bridging group or a single bond and preferably -COO-, -CONH-; a single bond, -O-, -S-, methylene, ethylene, propylene, and R ⁹ and R ¹⁰ are independently hydrogen, halogen, hydroxyl, carbocyclic or heterocyclic non-aromatic group or C ₁ -C ₃₀ alkyl; preferably X ¹⁴ is a single bond, or CF ₃ , OCF ₃ , F substituted or unsubstituted methylene, ethylene, propylene, butylene or pentylene and R ⁹ and R ¹⁰ are halogen or substituted or unsubstituted methylene, ethylene, propylene, and wherein at least one cyclohexyl group is connected to X or S ¹ or S ² in the compound of formula (IV).

Furthermore, preference is given to diamine groups D(IX-1)

wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently hydrogen, halogen, hydroxyl, a carbocyclic or heterocyclic non-aromatic group or a C ₁ -C ₃₀ alkyl group. Preferably, C ₁ -C ₃₀ alkyl is methyl, ethyl, propyl, butyl, pentyl or hexyl, 1,1'-cyclohexyl, 4-(C ₁ -C ₃₀ alkyl)-cyclohexyl, 3,4"-bis[4'-(C ₁ -C ₃₀ alkyl)-1,1'-di(cyclohexyl)-4-yl], 1,1'-di(cyclohexyl)-4-yl, 2-pyridine, pyrrolidine-2,5-dione, which is unsubstituted or substituted with CF ₃ , OCF ₃ , F, benzyl, pentyl, benzoate, 4-(phenoxycarbonyl), carboxylic acid, -SO ₃ H, -PO ₃ H, -OR ¹⁵ , wherein R ¹⁵ is C ₁ -C ₃₀ alkyl, preferably -C ₁₂ H ₂₅ ; unsubstituted or substituted benzyl, wherein the phenyl group is attached to X or S ¹ or S ² in the compound of formula (IV) ; Preferably, the two NH ₂ groups of (X-1) are at the meta or para position of the phenylene ring; further preferably, the structure of (X-1) is:

wherein R ¹¹ has the meaning and preferred embodiment as described above,

^X15 and ^X16 are independently a single bond or _C1 - _C30 alkyl, preferably _C1 - _C6 alkyl, -COO- and -CONH-; -COO( _C1 - _C6 alkylene)-, -CONH( _C1 - _C6 alkylene)-, and at least one phenyl group is connected to X or ^S1 or ^S2 in the compound of formula (IV).

More preferred diamine compounds (X) include 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, hexadecyloxy(3,5-diaminobenzoyl), and octadecyloxy(3,5-diaminobenzoyl).

Preferably, the diamine group D(XI) is of formula (XI-1)

wherein X ⁶ has the meaning and preference as described above, and preferably, for example, -O-, -S- or substituted or unsubstituted C ₁ -C ₆ alkylene, -O-(CH ₂ CH ₂ O) n-; -O-(C ₁ -C ₁₂ alkyl) nO-, -S-(C ₁ -C ₁₂ alkyl) nS-, triazine, 1,3,5-triazine-2,4,6-trione, 1,1'-cyclohexylene, NR ⁵ ((C ₁ -C ₆ alkyl) nNR ⁶ ), -(piperidine) n1-(C ₁ -C ₆ alkyl) n-(piperidine) n, wherein n is an integer from 1 to 6, and n1 is an integer from 0 to 6,

wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently of one another have the above-mentioned meanings and preferences, and wherein at least one phenyl group or X ⁶ is linked to X or S ¹ or S ² in the compound of formula (IV).

Furthermore, preferred diamine groups D(XI-1) are:

wherein R ¹¹ and R ¹² independently of one another have the meanings indicated above and are preferably hydrogen, C ₁ -C ₆ alkyl, hydroxy, or 4-(C ₁ -C ₃₀ alkyl)-cyclohexyl or 3,4"-bis[4'-(C ₁ -C ₃₀ alkyl)-1,1'-di(cyclohexyl)-4-yl], and wherein at least one phenyl group or X ⁶ is linked to X or S ¹ or S ² in the compound of formula (IV).

More preferred diamine groups D(XI) are as follows:

wherein n is independently 0 or 1 and R ³ , R ¹¹ , R ¹¹ , X ¹⁴ and X ¹⁷ have the same meanings and preferences as above, and wherein at least one phenyl or cyclohexyl group or X ¹⁷ is linked to X or S ¹ or S ² in the compound of formula (IV);

as well as

Even more preferred is the diamine group (XI)

4,4'-diaminodiphenyl, 4,4'-diaminodiphenyl-3,3'-dimethoxy, 4,4'-diaminodiphenyl-3,3'-dimethyl, 4,4'-diaminodiphenyl-3,3'-dihydroxy, 4,4'-diamino-diphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 4,4'-diaminodiphenylcarbonyl, 4,4'-diaminodiphenyloxamethylene, 4,4'-diaminodiphenyl-bis(trifluoromethyl)-methylene, 4,4'-diaminodiphenyl-bis(trifluoromethyl)-methylene Methyl-3,3'-dimethoxy or 4,4'-diaminodiphenyl-bis(trifluoromethyl)methylene-3,3'-dihydroxy, 4,4'-diaminodiphenyl ether, 4,4'-(p-phenyleneisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]-hexafluoro-propane, 2,2'-bis[4-(4-amino-2-trifluoro-methyl-phenoxy-)phenyl)hexafluoropropane, 4,4'-diamino-2,2'-di/trifluoromethyl)-biphenyl, 4,4'-bis[4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl.

Preferred are diamine groups D(XII) and (XIII) in which X ⁷ and X ⁸ , X ⁹ and X ¹⁰ or X ¹¹ are single bonds or C ₁ -C ₃₀ alkyl groups.

Preferably, X ⁷ and X ⁸ , X ⁹ and X ¹⁰ or X ¹¹ are independently of each other a single bond, -O-alkoxy-, such as -O-methylene-, methylene-O-; C1-C12 alkylene such as methylene, ethylene, propylene, butylene, pentylene or hexylene, substituted or unsubstituted 1,1'-cyclohexylene, -SO-, -S-, -SO ₂ -, -O-, -N(R ²⁵ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, 1,1'-cyclohexyl, substituted or unsubstituted 4-(C ₁ -C ₃₀ alkyl)-cyclohexyl, substituted or unsubstituted 3,4"-bis[4'-(C ₁ -C ₃₀ alkyl)-1,1'-di(cyclohexyl)-4-yl], 1,1'-di(cyclohexyl)-4-yl, wherein

R ¹¹ and R ¹² are preferably independently hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl;

Preferably, X ¹⁰ is -SO-, -SO ₂ -, -O-, -N(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, 1,1′-cyclohexyl, 4-(C ₁ -C ₃₀ alkyl)-cyclohexyl, 3,4″-bis[4′-(C ₁ -C ₃₀ alkyl)-1,1′-di(cyclohexyl)-4-yl] or 1,1′-di(cyclohexyl)-4-yl, and wherein X ⁹ and X ¹¹ are the same and are methylene, ethylene, propylene, butylene, pentylene, hexylene or -O-;

wherein n is an integer from 0 to 3, preferably, 0 or 1; and

If n is 0, X ⁹ and X ¹¹ are the same and are methylene, ethylene, propylene, butylene, pentylene, hexylene, -O-, -S-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -.

Further preferred diamine groups D of (XII) are:

wherein at least one phenyl group is connected to X, ^S1 or ^S2 in the compound of formula (IV).

Further preferred diamine groups D of (XIII) are:

wherein n is 0 or 1, and wherein ^X7 and ^X8 , ^X9 and ^X10 or ^X11 have the meanings and preferences given above, and wherein at least one phenyl group or X9 or ^X10 is linked to X or ^S1 or ^S2 in the compound of formula ( ^IV ).

Preferred diamine groups D(XIV) are 1,5-diaminonaphthalene and 2,7-diaminofluorene.

Preferred diamine groups D(XV) are the following compounds:

Furthermore, 1-cholesteryl-oxy-2,4-diamino-benzene, 1-cholestanyloxy-2,4-diaminobenzene, cholesteryloxy(3,5-diamino-benzoyl), cholesteryloxy(3,5-diaminobenzoyl).

Furthermore, the diamines described on page 10, lines 48 to 58 and page 11, lines 1 to 19 of EP-A-1,818,354 are incorporated by reference.

Preferably, more particularly most preferred is a compound of formula (XVI),

in

S ¹ , S ² , Z, U, y and z have the meanings and preferences described above for compound (IV); and R, R ¹ ′, R ^1″ independently represent hydrogen, methoxy, fluorine, nitrile and/or chlorine, provided that at least one of R, R ^1′ or R ^1″ is not hydrogen; preferably, R and R ^1′ have the meanings and preferences described above for compound (IVa); R ^1″ has the meanings and preferences described above for R ^1″ and R ^1″′ in compound (IVa);

Furthermore, more preferably, and more particularly most preferably, are compounds of formula (XXVc), (XXVd), (XXVe), (XXVf), (XXVg), (XVIIII), (XIX), and/or photo-alignment materials comprising a polymer having at least one side-substituted portion represented by formula (XXVc), (XXVd), (XXVe), (XXVf), (XXVg), (XVIIII), (XIX) on the side chain.

in

S ¹ , S ² , Z, U, y and z independently of one another have the meanings and preferences described above for compound (IV); and R ^1″ , R ^1″′ independently of one another represent hydrogen, methoxy, fluorine, nitrile and/or chlorine or U and the preferences for compound (IVa), with the proviso that at least one of R ^1″ or R ^1″′ is not hydrogen;

S ¹ , S ² , Z, U, y and z independently of one another have the meanings and preferences described above for compound (IV); and R ^1″ , R ^1″′ have the meanings and preferences described above for compound (IVa), and preferably independently of one another represent hydrogen, methoxy, fluorine, nitrile and/or chlorine or U, preferably hydrogen;

in

S ¹ , S ² , y, z, Z and U have the meanings given above for compound (IV) and preferably for the following (XVIIa), (XVIIb), (XVIIc), (XVIId), (XVIIf), and

R ^1′ , R ^1″ independently of one another represent hydrogen, methoxy, fluorine, nitrile and/or chlorine or U, preferably hydrogen.

Furthermore, preferred and even more particularly most preferred is a compound of formula (XVIII),

wherein U, S ² , S ¹ , Z, y and z have the meanings given above and preferably have the meanings given below for (XVIII) or (XIX); and

R, R ^1' , R ^1" independently represent hydrogen, methoxy, fluorine, nitrile and/or chlorine or U, provided that at least one of R ^1' , R ^1" is not hydrogen; wherein X ⁶ is a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₆ alkylene group;

wherein U, S ² , S ¹ , Z, y and z have the meanings given above and preferably have the meanings given below for (XVIII) or (XIX); and

R, R ^1′ , R ^1″ independently represent hydrogen, methoxy, fluorine, nitrile and/or chlorine or U, provided that at least one of R, R ^1′ , R ^1″ is not hydrogen; and wherein X ⁶ is a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₆ alkylene group.

In particular, the compound of the following formula is most preferred:

in

S ¹ , S ² , R ¹ , R ^1′ , R ^1″ , Z and U have the meanings and preferences given above; and y and z are each independently 1, 2, 3 or 4, preferably 1 or 2; more preferably y is 2 and z is 1; or z is 2 and y is 1; and even more preferably y and z are 1; or

R ¹ , R ^1′ , R ^1″ , Z and U have the meanings and preferences described above; and

S ¹ and S ² each independently of one another represent a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene group, preferably a C ₁ -C ₆ alkylene group, in particular a C ₁ -C ₂ alkylene group, and further in particular a C ₄ -C ₁₂ alkylene group; and wherein one or more, preferably non-adjacent, C-atoms, CH- or CH ₂ -, groups are replaced by at least one linking group, wherein the linking group is preferably a single bond, -O-, -O(CO), -S-, -(CO)O-, -C≡C-, or -NR ² - and more preferably a single bond, -O-, -O(CO) or -(CO)O- and most preferably -O-; most preferably S ¹ and S ² together represent a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene group, preferably a C ₁ -C ₆ alkylene group, in particular a C ₁ -C ₂ alkylene group, and further in particular a C ₄ -C ₁₂ alkylene group;

further

Particularly preferred and even more particularly most preferred are compounds of formula (XVIIb) or (XVIIc)

in

S ¹ , S ² , y, z, R ¹ , R ^1′ , R ¹ ″, Z and U have the meanings and preferences described above;

and

More particularly preferred are compounds of formula (XVIId) and (XVIIe)

in

S ¹ , S ² , R ¹ , R ^1′ , R ^1″ , Z and U have the above-mentioned meanings and preferences; and y and z are each independently of one another 1, 2, 3 or 4, preferably 1 or 2; more preferably y is 2 and z is 1; or z is 2 and y is 1; and further more preferably y and z are 1; most preferably S ¹ and S ² are each independently of one another a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene, preferably C ₁ -C ₆ alkylene, in particular C ₁ -C ₂ alkylene, and further in particular C ₄ -C ₁₂ alkylene; and wherein one or more, preferably non-adjacent, C-atoms, CH- or CH ₂ -groups are replaced by at least one linking group, wherein the linking group is preferably a single bond, -O-, -O(CO), -S-, -(CO)O-, -C≡C-, or, -NR ² -, and more preferably a single bond, -O-, -O(CO) or -(CO)O-, and most preferably -O-; in particular, most preferably ^S1 and ^S2 together are a single bond or a linear or branched, substituted or unsubstituted _C1 - _C12 alkylene, preferably _C1 - _C6 alkylene, especially _C1 - _C2 alkylene, and further especially _C4 - _C12 alkylene;

or

Furthermore, more particularly preferred is the compound (XVIIf)

in

R ¹ , R ^1′ , R ^1″ , Z and U have the meanings and preferences described above; and

Most preferably, S ² each independently of one another represents a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene, preferably C ₁ -C ₆ alkylene, in particular C ₁ -C ₂ alkylene; and wherein one or more, preferably non-adjacent, C-atoms, CH- or CH ₂ -groups may be replaced by at least one linking group, wherein the linking group is preferably a single bond, -O-, -O(CO), -S-, -(CO)O-, -C≡C- or -NR ² -, and more preferably a single bond, -O-, -O(CO) or -(CO)O-, and most preferably -O-; in particular, most preferably S ¹ and S ² together represent a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene, preferably C ₁ -C ₆ alkylene, in particular C ₁ -C ₂ alkylene, and further in particular C ₄ -C ₁₂ alkylene;

or

Furthermore, more particularly preferred are compounds of formula (XVIII) or (XIX) which are even more particularly preferred.

And preferably, compound (XIX) is a compound of formula (XVIIIa), and compound (XVIII) is a compound of formula (XIXa), (XVIIIa) or (XVIIIb)

wherein R ¹ , R ^1′ , R ^1″ , Z and U have the meanings and preferences described above; and

S ¹ and S ² each independently represent a single bond or a spacer unit, which is a cyclic, linear or branched, substituted or unsubstituted C ₁ -C ₂₄ alkylene group, preferably C ₁ -C ₁₂ alkylene group, more preferably C ₁ -C ₆ alkylene group, such as methylene, ethylene, linear or branched propylene, butylene, pentylene or hexylene group, wherein one or more, preferably non-adjacent, C-atoms, CH- or CH ₂ -groups may be replaced by at least one linking group, wherein the linking group is preferably a single bond, -O-, -O(CO), -S-, -(CO)O-, -C≡C-, or -NR ² - and, more preferably a single bond, -O-, -O(CO) or -(CO)O-, and most preferably -O-, and wherein the substituent is preferably at least one C ₁ -C ₆ alkyl group, preferably methyl; and/or S ¹ and S 2 ² each independently of one another represents a non-aromatic, aromatic, unsubstituted or substituted carbocyclic or heterocyclic group of formula (V):

-(Z ^1a ') _a3' -(Z ¹ -C ¹ ) _a1 -(Z ² -C ² ) _a2 -(Z ^1a ) _a3 -(V)

in:

C ¹ and C ² each independently represent an alicyclic or aromatic, unsubstituted or substituted carbocyclic or heterocyclic group, preferably C ¹ and C ² are linked at opposite positions via a bridging group Z ¹ , Z ² , Z ^1a and/or Z ^1a ' so that the groups S ¹ and/or S ² have a long molecular axis, and

Z ¹ , Z ² , Z ^1a , and Z ^1a ′ each independently represent a bridging group having the above-mentioned meanings and preferences, and

a1, a3', a2, and a3 each independently represent an integer from 0 to 3, such that

a1+a3'+a2+a3≤6, preferably a3 or/and a3' is 1 and a1+a2≤4,

Most preferably, S ¹ and S ² each independently of one another represent a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene group, preferably a C ₁ -C ₆ alkylene group, in particular a C ₁ -C ₂ alkylene group, further in particular a C ₄ -C ₁₂ alkylene group; and wherein one or more, preferably non-adjacent, C-atoms, CH- or CH ₂ -groups may be replaced by at least one linking group, wherein the linking group is preferably a single bond, -O-, -O(CO), -S-, -(CO)O-, -C≡C-, or -NR ² - and more preferably a single bond, -O-, -O(CO)- or -(CO)O- and most preferably -O-; in particular, most preferably, S ¹ and S ² together represent a single bond or a linear or branched, substituted or unsubstituted C ₁ -C ₁₂ alkylene group, preferably a C ₁ -C ₆ alkylene group; and

y and z are each independently 1, 2, 3 or 4, preferably 1 or 2; more preferably y is 2 and z is 1; or z is 2 and y is 1; and further more preferably y and z are 1; ^X6 is preferably a single bond or a linear or branched, substituted or unsubstituted _C1 - _C6 alkylene group, preferably a linear or branched propylene, butylene, pentylene or hexylene group connected once or twice to the side chain, in particular wherein the propylene group is connected once at the 2-position or twice at the 2,2'-position, and the butylene group is connected once or twice at the 2- and/or 3-position.

More preferably, still more particularly, most preferably, a compound having at least one side-substituted portion represented by formula (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVa) or (XXVb) and/or a photo-alignment material, the photo-alignment material comprising a polymer having at least one side-substituted portion represented by formula (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVa) or (XXVb) on the side chain.

Among them, (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVa)

U and Z independently have the above-mentioned meanings and preferences, and

R ^1' , R ^1" and R ^1"' independently represent hydrogen, methoxy, fluorine, nitrile and/or chlorine, preferably R ^1' , R ^1" are hydrogen, and R ^1"' is hydrogen, methoxy, fluorine, nitrile and/or chlorine,

in

U and Z independently have the above-mentioned meanings and preferences, and Z is preferably -OCO-, _-OCH2- or a single bond. In a further preferred embodiment, Z is _-OCH2- or a single bond, and R1 ^" and R1 ^'" independently represent hydrogen, methoxy, fluorine, nitrile and/or chlorine, provided that at least one of R1 ^" or ^R1'" is not hydrogen.

Still further preferred are polymers having at least one pendant substituted moiety represented by formula (XXII), (XXIV), (XXV), (XXVa), or (XXVb) on the side chain.

Furthermore, the present invention relates to a process for the preparation of polymers comprising contacting, preferably polymerizing, a compound of the present invention comprising at least one pendant substituted moiety represented by formula (I), in particular a monomeric compound, optionally in the presence of a solvent.

The solvents used in the context of the present invention are aprotic or protic polar solvents, γ-butyrolactone, dimethyl sulfoxide, N,N-dimethylacetamide, chlorobenzene, diethylene glycol diethyl ether, toluene, chloroform, chlorobenzene, diethylene glycol diethyl ether, diisobutyl ketone, methyl cellosolve, butyl cellosolve, butyl carbitol, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide, methyl ethyl ketone (MEK), 1-methoxypropyl acetate (MPA), alcohols, in particular 1-methoxypropanol (MP). Preference is given to aprotic polar solvents, in particular γ-butyrolactone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or N,N-dimethylformamide, methyl ethyl ketone (MEK), 1-methoxypropyl acetate (MPA).

Polymers, in particular polyamic acids, polyamic acid esters and polyimides and mixtures thereof can be prepared according to known methods, such as those described in Plast. Eng. 36 (1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc. and in WO 2007/071091, page 64, second paragraph to page 68, line 29.

Preferably, the polyamic acid, polyamic acid ester and polyimide and mixtures thereof are prepared by reacting at least one tetracarboxylic dianhydride in contact with at least one monomeric compound of the present invention, the monomeric compound of the present invention comprising at least one pendant substituted moiety represented by formula (I) having two diamino groups as polymerizable groups, a diamino group, and

In general, polyamic acids, polyamic acid esters, polyimides, and mixtures thereof are prepared by polycondensation and dehydration reactions that can be carried out in one step or two steps.

Typically, at least one monomeric compound of the present invention comprising at least one side-substituted moiety represented by formula (I) and comprising a polymerizable diamino group is polycondensed with at least one tetracarboxylic dianhydride to preferably form a polyamic acid or polyamic acid ester, and then dehydrated to preferably form the corresponding polyimide, or a mixture of polyamic acid, polyamic acid ester and polyimide.

More preferably, the present invention relates to a process wherein, after polycondensation, thermal cycling is performed and water is removed during polyimide formation.

More preferably, the present invention relates to a process wherein the imidization is carried out before or after application of the polymer, copolymer or oligomer to the support, wherein irradiation with coordinated light is preferably carried out.

In the context of the present invention, the term "polyimide" refers to a partially or fully imidized polyamic acid or polyamide ester. Similarly, the term "imidized" in the context of the present invention refers to partially or fully imidized.

Examples of materials that can be used for dehydration include acetic anhydride, trifluoroacetic anhydride, or propionic anhydride. Examples of materials that can be used for the ring-opening catalyst include trimethylamine, pyridine, or collidine. Polyamic acid esters are obtained by reacting, for example, the above-mentioned polyamic acid with an organic halide, alcohol, or phenol.

The tetracarboxylic dianhydride used in the present invention is not particularly limited and represents, for example, a compound of formula (XXIII)

in:

T represents a tetravalent organic group.

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

Preferred aliphatic or alicyclic tetracarboxylic dianhydrides or mixtures thereof are: 1,1,4,4-butanetetracarboxylic dianhydride, ethylene maleic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, exo-2,3,5-tricarboxycyclopentylacetic dianhydride, mixtures containing at least 90% exo-2,3,5-tricarboxycyclopentylacetic dianhydride, tetrahydro-4,8-methanefuro[3,4-d]oxepin-1,3,5 ,7-tetraketone, 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-tetraketone, 3,5,6-tricarboxy-norbornylacetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, back-[1S,5R,6R]-3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran 2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 1,8-dimethylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride , 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic 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 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 dianhydride, 4-tert-butyl-6-(2,5-dicarboxyphenoxy)-diphenylpropane dianhydride oxotetrahydro-3-furyl)-2-benzofuran-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-5-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-6-methylhexahydro-2-benzofuran-1,3-dione Ketone, 5-(2,5-dioxotetrahydro-3-furyl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione, 6-(2,5-dioxotetrahydro-3-furyl)-4-methylhexahydro-2-benzofuran-1,3-dione, 9-isopropyloctahydro-4,8-ethanefuro[3',4':3,4]cyclobutane[1,2-f][2]benzofuran-1,3,5,7-tetraone, 1,2,5,6-cyclooctanetetracarboxylic dianhydride, octahydro-4 ,8-ethanefuro[3',4':3,4]cyclobutane[1,2-f][2]benzofuran-1,3,5,7-tetraone, octahydrofuro[3',4':3,4]cyclobutane[1,2-f[2]benzofuran-1,3,5,7-tetraone, tetrahydro-3,3'-difuran-2,2',5,5'-tetraone, 4,4'-oxybis(1,4-phenylene)bis(phthalic acid) dianhydride, and 4,4'-methylenebis(1,4-phenylene)bis(phthalic acid) dianhydride.

Examples of preferred aromatic tetracarboxylic dianhydrides are:

Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 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'-oxybis(1,4-phenylene)bis(phthalic acid) dianhydride, 4,4'-methylenebis(1,4-phenylene)bis(phthalic acid) dianhydride, 4-tert-butyl-6-(2,5-dioxotetrahydro-3-furyl)-2-benzofuran-1,3-dione, etc.

More preferred tetracarboxylic dianhydrides for forming the tetravalent organic group T are selected from:

1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, tetrahydro-4,8-methanefuro[3,4-d]oxepin-1,3,5,7-tetraone, 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-tetraone, 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, pyromellitic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic dianhydride benzofuran-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-5-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione, 4-tert-butyl-6-(2,5-dioxotetrahydro-3-furyl)-2-benzofuran-1,3-dione, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

More preferred tetracarboxylic dianhydrides for forming the tetravalent organic group T are selected from:

1,2,3,4-Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, exo-2,3,5-tricarboxycyclopentylacetic dianhydride, mixtures containing at least 90% exo-2,3,5-tricarboxycyclopentylacetic dianhydride; tetrahydro-4,8-methanefuro[3,4-d]oxepin-1,3,5,7-tetraone, 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-tetraone, 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, pyromellitic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride 1,2-dicarboxylic acid dianhydride, 5-(2,5-dioxotetrahydro-3-furyl)-5-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, tetrahydro-3-furyl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione, 4-tert-butyl-6-(2,5-dioxotetrahydro-3-furyl)-2-benzofuran-1,3-dione, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

Furthermore, the present invention relates to a composition, preferably a blend and/or formulation, comprising a photoalignment material or polymer according to the present invention having at least one side-substituted moiety represented by formula (I) on the side chain, or a process according to the present invention or prepared by the process according to the present invention, and/or at least one compound comprising at least one side-substituted moiety represented by formula (I). Preferred compositions of the present invention comprise

- optionally at least two different tetracarboxylic dianhydrides, and compound (I) as described above and with the given preferences, wherein the polymerizable group is an amine; and/or

- optionally at least two different compounds (I) as described above and with the given preferences, and wherein preferably the polymerizable group is an amine, preferably two amine groups;

- optionally a compound (I) as described above and with the given preferences, wherein the polymerizable group is an amine and at least one further diamine according to the invention, which is not attached to a side chain of formula (I). Preferably, not attached to a side chain (I), the diamine is saturated with hydrogen at the potential attachment position,

Optionally a solvent as described above, and/or

-Optional additives as described below.

A more preferred composition of the present invention is a formulation comprising a solvent having the following description and preferences, but not limited thereto, and in particular, further comprising additives having the following description and preferences.

In addition, the composition of the present invention optionally comprises an additive, such as a crosslinking agent, such as epoxy, acrylate, methacrylate reagents, for example, the photoalignment additives disclosed in US 2009/0290109; or an additive selected from the following: 4,4'-methylene-bis(N,N-diglycidylaniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1,2,4,5-N,N'-diglycidyl diimide, polyethylene glycol diglycidyl ether and N,N-diglycidylcyclohexylamine.

Preferably, the composition of the present invention comprises 0.5% to 99% by weight of a photo-alignment material having at least one side-substituted moiety represented by formula (I) on its side chain and 99.5% to 1% by weight of an organic solvent. Preferably, the composition comprises 0.5% to 40% by weight, more preferably 0.5% to 10% by weight, and most preferably 0.5% to 5% by weight of a photo-alignment material having at least one side-substituted moiety represented by formula (I) on its side chain.

Furthermore, the present invention relates to polymers, preferably copolymers, comprising a polymer having at least one side-substituted moiety represented by formula (I) on a side chain, and/or a compound comprising at least one side-substituted moiety represented by formula (I), preferably a copolymer of the present invention comprising

at least two different tetracarboxylic dianhydrides and a compound (I) as described above and with the given preferences, wherein the polymerizable group is an amine; and/or

at least two different compounds (I) as described above and with the given preferences, and in which preferably the polymerizable group is an amine, preferably two amine groups;

- Compound (I) as described above and with the given preferences, wherein the polymerizable group is an amine, and at least one further diamine according to the invention, which is not attached to a side chain of formula (I). Preferably, without being attached to a side chain (I), the diamine is saturated with hydrogen at such potential attachment positions.

In a further embodiment, the present invention relates to a photoalignment material, preferably a polymer having at least one pendant substituted moiety represented by formula (I) on a side chain, which can be obtained by the method as described above, and preferably obtained by the method as described above.

The polymers according to the present invention can be used in the form of a polymer layer, preferably a photoalignment layer or in particular an orientation layer, alone or in combination with other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers and/or photoactive monomers, depending on the application in which the polymer or oligomer layer is incorporated. It will be appreciated that by varying the composition of the polymer layer, specific and desired properties such as incident pretilt angle, good surface wetting, high voltage retention ratio or specific anchoring energy can be controlled.

In the context of the present invention, the expression polymer layer means an oligomer, homopolymer or copolymer layer.

Furthermore, the present invention relates to a polymer layer, in particular an alignment layer, comprising at least one photoalignment material having at least one side-substituted portion represented by formula (I) as described in the present invention on its side chain, or comprising at least one polymer obtained or prepared in the present invention, or a polymer layer prepared as described in the present invention.

Polymer layers can be readily produced from the polymers or oligomers of the invention, and a further embodiment of the invention relates to polymer layers comprising the polymers according to the invention, preferably produced by treatment with aligning light.

Preferably, the present invention relates to a method for preparing a polymer layer, in particular an alignment layer, comprising applying a photoalignment material or polymer obtained or prepared as described in the present invention, or a composition of the present invention to a support, and treating it with aligning light.

The polymer layer is preferably prepared by applying one or more polymers according to the invention to a support and, after imidization or without imidization, treating the polymer or a composition comprising the polymer by irradiation with aligning light.

The treatment with aligning light can be performed in a single step or in several separate steps. In a preferred embodiment of the invention, the treatment with aligning light is performed in a single step.

In the context of the present invention, aligning light is light having a wavelength that can induce photoalignment. Preferably, the wavelength is in the UV-A, UVB, and/or UV/C range, or in the visible light range. The appropriate wavelength depends on the photoaligning compound. Preferably, the photoreactive group is sensitive to visible and/or UV light. A further embodiment of the present invention relates to generating the aligning light by laser.

The instantaneous direction of the aligning light can be perpendicular to the substrate or at any oblique angle.

In order to generate the tilt angle, it is preferable to expose the aligning light at an oblique angle.

More preferably, the aligning light is at least partially linearly polarized, elliptically polarized, for example circularly polarized, or unpolarized; most preferably, it is at least circularly or partially linearly polarized light, or unpolarized light applied by oblique exposure. In particular, the most preferred aligning light is significantly polarized light, especially linearly polarized light; or the aligning light is unpolarized light applied by oblique irradiation.

In a more preferred embodiment of the present invention, the polymer, copolymer or oligomer is treated with polarized light, in particular linearly polarized light, or with unpolarized light by oblique irradiation.

Typically, the support is a transparent support such as a glass or plastic substrate, optionally coated with indium tin oxide (ITO).

Furthermore, the tilt angle and orientation direction within the polymer layer can be altered by controlling the irradiation direction of the aligning light. It is understood that by selectively irradiating a specific region of a polymer layer, that specific region of the layer can be oriented. This allows for the provision of a layer with a defined tilt angle. The induced orientation and tilt angle are maintained within the polymer layer through specific processes, particularly crosslinking.

A further preferred method of the present invention involves

- a method for producing a vertically aligned polymer layer;

- A method for preparing a multi-domain vertically aligned polymer layer;

- A method for producing a polymer layer having a tilted optical axis.

A further embodiment of the present invention relates to a polymer layer, in particular an alignment layer, comprising at least one photoalignment material as described above or obtained as described above having at least one pendant substituted moiety represented by formula (I) in a side chain.

The polymer layer comprises at least one photo-alignment material having at least one pendant substituted moiety represented by formula (I) on a side chain as described above.

It will be appreciated that the polymer layers (polymer gels, polymer networks, polymer films, etc.) of the present invention can also be used as orientation layers for liquid crystals. A further preferred embodiment of the present invention relates to an orientation layer comprising one or more polymers or oligomers according to the present invention, preferably in cross-linked form. Such an orientation layer can be used to produce non-structural or structured optical or optoelectronic components, preferably hybrid layer components.

Furthermore, the present invention relates to a process for preparing polymers, wherein one or more polymers, copolymers or oligomers according to the invention are preferably coated onto a support from a solution of the polymer or oligomeric material, and the solvent is subsequently evaporated, wherein, after any imidization step which may be required, the polymer or oligomer or polymer composition is treated with aligning light, preferably isomerized and/or crosslinked by irradiation with aligning light.

Preferred methods of the present invention relate to methods wherein the direction of orientation and tilt within a polymer layer is altered by controlled irradiation with aligning light and/or by selectively irradiating specific areas of the polymer layer, which are aligned.

The alignment layer is suitably prepared from a solution of a photoalignment material. The polymer solution is applied to a support optionally coated with an electrode [e.g., a glass plate coated with indium tin oxide (ITO)] to produce a homogeneous layer 0.05-50 μm thick. In this process, different coating techniques can be used, such as spin coating, meniscus coating, line coating, slit coating, lithography, offset printing, gravure printing. Then, or optionally after the previous imidization step, for example, a high-pressure mercury vapor lamp, a xenon lamp, or a pulsed UV laser is used to irradiate the area to be oriented, using a polarizer and a mask optionally for generating a structural pattern.

Furthermore, the present invention relates to the use of the polymer layer according to the invention, preferably in crosslinked form, as an alignment layer for liquid crystals.

Furthermore, the present invention relates to preferred polymer layers for inducing vertical alignment of adjacent liquid crystal layers, in particular for operating the optical cell in MVA mode.

The irradiation time depends on the output of the respective lamp and can be from a few seconds to several hours.However, the photoreactions (dimerization, polymerization, crosslinking) can also be carried out by irradiating the homogeneous layer using, for example, a filter which only passes the radiation suitable for the crosslinking reaction.

In addition, the present invention relates to the use of the photoalignment material described in the present invention, or the polymer having at least one side substitution portion represented by formula (I) on the side chain or prepared according to claims 1 and 8 for preparing a polymer layer, especially an alignment layer.

The invention further relates to the use of the polymer layer described in the invention, as described in the invention, or produced as described in the invention, or the photoalignment material described in the invention, for producing optical and optoelectronic non-structural or structural components, preferably liquid crystal display units, security devices, multi-layer and hybrid layer components.

It will be appreciated that the polymer layers of the present invention can be used to produce optical or optoelectronic devices having at least one orientation layer, as well as unstructured and structured optical elements and multilayer systems.

The present invention relates to the use of a polymer layer as a liquid crystal alignment layer, preferably for inducing vertical alignment of adjacent liquid crystal layers.

A further embodiment of the present invention relates to an optical or optoelectronic device comprising one or more polymers or oligomers according to the present invention.

In particular, the present invention relates to optical and optoelectronic non-structural or structural components, preferably liquid crystal display units, security devices, multi-layer and hybrid layer components, which contain at least one polymer layer as described in the present invention or produced as described in the present invention, or contain at least one photoalignment material as described in the present invention.

The optoelectronic device may comprise more than one layer.

Furthermore, the present invention relates to an optoelectronic nonstructural or structural component, as described in the present invention, which is a liquid crystal display unit comprising at least one polymer layer as described in the present invention or prepared as described in the present invention, or comprising at least one photoalignment material as described in the present invention.

A layer, or each layer, may contain one or more regions of different spatial orientation.

In the present invention, the expression optical or optoelectronic element means, for example, a multilayer system, or a device for producing a display waveguide, a security or brand protection element, a barcode, an optical grating, an optical filter, a retarder, a compensation film, a reflective polarizing film, an absorbing polarizing film, an anisotropic scattering film compensator and a retarder film, a twisted retarder film, a cholesteric liquid crystal film, a guest-host liquid crystal film, a monomer conjugated film, a smectic liquid crystal film, a polarizer, a piezoelectric cell, a film with nonlinear optical properties, a decorative optical element, a brightness enhancement film, a component for wavelength band selective compensation, a component for multidomain compensation, a component for a multi-viewing angle liquid crystal display, a color retarder, a polarization state correction/regulation film, a component for an optical or optoelectronic sensor, a component for a brightness enhancement film, a component for an optical-based communication device, a device having G/H-polarizers with anisotropic absorbers, reflective circular polarizers, reflective linear polarizers, MC (monomeric conjugated films), liquid crystal displays, preferably twisted nematic (TN) liquid crystal displays, (RTN) reverse TN, (VATN), (VECB), hybrid alignment nematic (HAN) liquid crystal displays, electrically controlled birefringence (ECB) liquid crystal displays, super twisted nematic (STN) liquid crystal displays, optionally compensated birefringence (OCB) liquid crystal displays, π-cell liquid crystal displays, flat panel switching (IPS) liquid crystal displays, fringe field switching (FFS) liquid crystal displays, vertically aligned (VA) (preferably (MVA=multidomain vertical alignment)) liquid crystal displays; all of the above display types are used in transmissive or reflective or transflective mode.

The advantages of the present invention could not be foreseen by those skilled in the art.

Surprisingly, it was found that the introduction of pendant substituents at peripheral positions of polymer side groups with specific molecular architecture plays an important role in obtaining MVA materials with optimized properties, such as the desired high-voltage holding ratio, the tunable pretilt angle required for the MVA mode and their stability to light and heat.

In particular, it was found that the use of the novel optical alignment materials of the present invention achieved the desired change in the pretilt angle of the liquid crystal without interfering with the parameter settings of UV exposure energy and incident angle, thus eliminating the need for time-consuming modifications to the production line.

Example

Definitions used in the embodiments:

Mass spectrometry EI = EI (electron impact)

¹ H NMR = ¹ H nuclear magnetic resonance spectrum analysis

DMSOd ₆ = deuterated dimethyl sulfoxide

300MHz＝300 MHz

M ⁺ = molecular mass of the cation

m = multiplet

d = doublet

dd = double doublet

t = triplet state

s = singlet state

q = quartet

br＝broad

HCl = Hydrogen chloride

NaOH = Sodium Hydroxide

NMP = N-methyl-2-pyrrolidone

THF = Tetrahydrofuran

Pretilt = tilt of liquid crystal

synthesis

The preparation of 6-hydroxyhexyl-3,5-dinitrobenzoate and 2-(2,4-dinitrophenyl)ethanol was carried out as described in WO 2007/071091 A1, pages 79 and 92, which is hereby incorporated by reference.

Example 1/Preparation of Compound 1

2-Fluoro-4-(4,4,4-trifluorobutoxy)benzonitrile

464.5 g (1.95 mol) of 4-iodo-1,1,1-trifluorobutane, 267.6 g (1.95 mol) of 4-nitrile-3-fluorophenol, and 539.5 g (3.90 mol) of potassium carbonate were dissolved in 3 L of NMP. The mixture was heated to 80°C overnight. The solution was cooled to room temperature, and the reaction mixture was extracted with ethyl acetate and water. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 503 g of compound 1.

Example 2/Preparation of Compound 2

2-Fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid

61.8 g (250.0 mmol) of compound 1 was heated to reflux for 2 days in 150 mL of sulfuric acid, 600 mL of acetic acid, and 400 mL of hydrochloric acid. The mixture was cooled and poured into 2.5 L of water. The solid was filtered and washed with water. The solid was dried under vacuum to yield 53.4 g of compound 2.

Example 3/Preparation of Compound 3:

4-Formylphenyl 2-fluoro-4-(4,4,4-trifluorobutoxy)benzoate

5.0 g (18.7 mmol) of compound 2, 2.29 g (18.78 mmol) of 4-hydroxybenzaldehyde, and 0.23 g (1.88 mmol) of 4-dimethylaminopyridine were dissolved in 25 mL of dichloromethane. 3.88 g (18.78 mmol) of dicyclohexylcarbodiimide (DCC) were added at 0°C. The solution was stirred at 0°C for 1 hour and at room temperature overnight. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to yield 6.92 g of compound 3.

Example 4/Preparation of Compound 4:

(2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)prop-2-enoic acid

6.92 g (18.68 mmol) of compound 3 and 3.32 g (31.93 mmol) of malonic acid were dissolved in 15 ml of pyridine. 0.78 ml (9.39 mmol) of pyrrolidine was added to the suspension and allowed to react at 90° C. under argon for 2.5 hours. The yellow solution was then poured into ice. The solution was gradually acidified to pH 1-2 with 25% HCl solution and stirred for 15 minutes. The product was filtered off and dried under vacuum at room temperature to obtain 7.75 g of compound 4.

Example 5/Preparation of Compound 5:

2-Fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid 4-{(1E)-3-[2-(2,4-dinitrophenyl)ethoxy]- 3-Oxoprop-1-enyl)phenyl ester

2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 4.86 g (11.8 mmol) of compound 4, and 144 mg (1.2 mmol) of 4-dimethylaminopyridine were dissolved in 30 mL of dichloromethane. 2.48 g (13.0 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) were added at 0°C. The solution was stirred at 0°C for 1 hour and at room temperature overnight. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was chromatographed on 200 g of silica gel using a 95:5 toluene:ethyl acetate eluent and crystallized from an ethyl acetate:hexane mixture to yield 5.08 g (71%) of compound 5 as colorless crystals.

Example 6/Preparation of Compound 6:

2-Fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid 4-{(1E)-3-[2-(2,4-diaminophenyl)ethoxy]- 3-Oxoprop-1-enylphenyl ester

5.8 g (8.38 mmol) of compound 5 were dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml of water. 13.9 g (51.4 mmol) of ferric chloride hexahydrate were added. 5.60 g (85.7 mmol) of zinc powder were added in portions over 60 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was partitioned between ethyl acetate and water and filtered. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was filtered over 200 g of silica gel using a 1:3 toluene:ethyl acetate eluent and crystallized from an ethyl acetate:hexane mixture to produce 3.30 g of compound 6 as colorless crystals.

Example 7/Preparation of Compound 7

3-Methoxy-4-(pentyloxy)benzoic acid

16.57 g (109.7 mmol) of bromopentane, 20 g (109.7 mmol) of methyl vanillate and 30.30 g (219 mmol) of potassium carbonate were dissolved in 200 mL of NMP. The mixture was heated to 80° C. overnight. 100 ml (100 mmol) of 1N NaOH solution was added to the above mixture. The suspension was heated at reflux temperature for 30 minutes until the reaction was complete. The reaction mixture was allowed to cool at room temperature and plunged into cold water. The solution was gradually acidified with 25% HCl solution and stirred for 15 minutes. The product was filtered off, washed with water and dried under vacuum at room temperature overnight to obtain 23.90 g (97%) of compound 7 as a white solid.

Example 8/Preparation of Compound 8

2,3-Difluoro-4-(pentyloxy)benzoic acid

19.09 g (109.7 mmol) of 2,3-difluoro-4-hydroxybenzoic acid was refluxed in 500 ml of methanol and 2 drops of sulfuric acid for 22 hours. The solvent was evaporated under vacuum. To the residue were added 16.57 g (109.7 mmol) of bromopentane, 30.30 g (219 mmol) of potassium carbonate and 200 ml of NMP. The mixture was heated to 80° C. overnight. 100 ml (100 mmol) of 1N NaOH solution was added to the above mixture. The suspension was heated at reflux temperature for 30 minutes until the reaction was complete. The reaction mixture was cooled at room temperature and poured into cold water. The solution was gradually acidified with 25% HCl solution and stirred for 15 minutes. The product was filtered off, washed with water and dried under vacuum at room temperature overnight to obtain 25.72 g (96%) of compound 8 as a white solid.

Example 9/Preparation of Compound 9/3-Fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid

4.37 g (28.00 mmol) of 3-fluoro-4-hydroxybenzoic acid was refluxed in 100 ml of methanol and 2 drops of sulfuric acid for 22 hours. The solvent was evaporated under vacuum. To the residue were added 6.66 g (28.00 mmol) of 4-iodo-1,1,1-trifluorobutane, 11.84 g (85.00 mmol) of potassium carbonate and 50 ml of NMP. The mixture was heated to 80°C overnight. 40 ml (40 mmol) of 1N NaOH solution was added to the above mixture. The suspension was heated at reflux temperature for 30 minutes until the reaction was complete. The reaction mixture was cooled at room temperature and poured into cold water. The solution was gradually acidified with 25% HCl solution and stirred for 15 minutes. The product was filtered off, washed with water and dried under vacuum at room temperature overnight to obtain 5.91 g (79%) of compound 9 as a white solid.

4-Formylphenyl compounds 3A, 3B, and 3C, each carrying compounds 7, 8, and 9 as an ester substituent, were prepared according to the method described in Example 3 of compound 3, with the proviso that compound 2 was replaced by compound 7, compound 8, and compound 9, respectively:

4-Formylphenyl 3-methoxy-4-(pentyloxy)benzoate 3A

4-Formylphenyl 2,3-difluoro-4-(pentyloxy)benzoate 3B

4-Formylphenyl 3-fluoro-4-(4,4,4-trifluorobutoxy)benzoate 3C

Cinnamic acid compounds 4A, 4B, and 4C were prepared according to the method described in Example 4 of compound 4, with the proviso that compound 3 was replaced by compound 3A, compound 3B, and compound 3C, respectively:

(2E)-3-(4-{[3-methoxy-4-(pentyloxy)benzoyl]oxy}phenyl)prop-2-enoic acid 4A

(2E)-3-(4-{[2,3-difluoro-4-(pentyloxy)benzoyl]oxy}phenyl)prop-2-enoic acid 4B

(2E)-3-(4-{[3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)prop-2-enoic acid 4C

Dinitro compounds 5A, 5B, and 5C were prepared according to the method described in Example 5 of compound 5, with the following conditions: compound 4 was replaced by compound 4A and 2-(2,4-dinitrophenyl)ethanol was replaced by 6-hydroxyhexyl-3,5-dinitrobenzoate, and compound 4B and 2-(2,4-dinitrophenyl)ethanol were replaced by 6-hydroxyhexyl-3,5-dinitrobenzoate and compound 4C, respectively:

4-[(1E)-3-({6-[(3,5-dinitrobenzoyl)oxy]hexyl}oxy)-3-oxoprop-1-enyl]phenyl 3-methoxy-4-(pentyloxy)benzoate 5A

4-[(1E)-3-({6-[(3,5-dinitrobenzoyl)oxy]hexyl}oxy)-3-oxoprop-1-enyl]phenyl 2,3-difluoro-4-(pentyloxy)benzoate 5B

4-{(1E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl 3-fluoro-4-(4,4,4-trifluorobutoxy)benzoate 5C

Compound 11 was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 5A.

Compound 12 was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 5B.

Compound 10 was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 5C.

Polymerization step A (formation of polyamic acid)

Example 10:

0.820 g (3.66 mmol) of 2,3,5-tricarboxycyclopentylethane-1,2:3,4-dianhydride was added to a solution of 2.000 g (3.66 mmol) of compound 6 in 6.56 mL of NMP. The mixture was then stirred at 0°C for 2 hours. The mixture was then allowed to react at room temperature for 21 hours. The polymer mixture was diluted with 18 mL of THF, precipitated in 800 ml of water, and dried under vacuum at room temperature to produce 2.76 g of polyamic acid 1 in the form of a white powder: [h] = 0.21 dL/g

Example 11:

Similar to Example 10, the following diamines and 2,3,5-tricarboxycyclopentylethane-1,2:3,4-dianhydride were used to prepare polyamic acid.

Compound 10

Produced polyamic acid 2 as a white powder; [η] = 0.22 dL/g

Compound 11

Produced polyamic acid 7 as a white powder; [η] = 0.26 dL/g

Compound 12

Produced polyamic acid 8 as a white powder; [η] = 0.27 dL/g

Example 12:

Similar to Example 10, the following diamines and 1,2,3,4-cyclobutanetetracarboxylic dianhydride were used to prepare polyamic acid.

Compound 6

Produced polyamic acid 5 as white powder; [η] = 0.28 dL/g

Compound 10

Produced polyamic acid 6 as white powder; [η] = 0.29 dL/g

Compound 11

Produced polyamic acid 3 as white powder; [η] = 0.33 dL/g

Compound 12

Produced polyamic acid 4 as white powder; [η] = 0.40 dL/g

Example 13:

Similar to Example 10, the following tetracarboxylic dianhydride mixture and Compound 6 were used to prepare polyamic acid.

A mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentylethane-1,2:3,4-dianhydride in a 25:75 (molar ratio) yielded polyamic acid 9 as a white powder; [η] = 0.31 dL/g

Example 14:

Polymerization step B (formation of polyimide)

The 0.50g polyamic acid 3 that obtains in above embodiment 12 is dissolved in 3ml 1-methyl-2-pyrrolidine (NMP).To wherein adding 0.28g (3.57mmol, 4 equivalents) pyridine and 364mg (3.57mmol, 4 equivalents) diacetic anhydride, dehydration and ring closure were carried out 2 hours at 80 ℃.Polymer mixture is diluted with 1.5ml NMP, precipitated in 100ml diethyl ether, collected by filtration.After room temperature is dried under vacuum, polymer is reprecipitated into 200ml water from THF (10ml), produces 0.45g polyimide 1; [η]=0.31dL/g, imidization degree ID=100%

The following polyamic acid was used to prepare partially imidized polyimide similar to the polymerization steps of Example 12. The ratio of acetic anhydride to pyridine was used to adjust the degree of imidization.

Polyamic acid 3 and 1.2 equivalents of acetic anhydride and pyridine produced polyimide 2 as a white powder; [η] = 0.33 dL/g, ID = 35%.

Example 15:

A liquid crystal cell was prepared in which the liquid crystal was aligned by the photoreactive polyamic acid 1.

A 4% solution of polyamic acid 1 was prepared by mixing solid polyamic acid 1 in a solvent, N-methyl-2-pyrrolidone (NMP), and stirring thoroughly until the solid polyamic acid 1 was dissolved, and adding a second solvent, butyl cellulose (BC), and stirring the entire composition thoroughly to obtain a final solution. The solvent ratio between N-methyl-2-pyrrolidone and butyl cellulose was 1:1. The above polymer solution was spin-coated on two ITO-coated glass substrates at a rotation speed of 1200 rpm for 30 seconds. After spin coating, the substrates were subjected to a baking process, including pre-baking at 130°C for 5 minutes and post-baking at a temperature of 200°C for 40 minutes. The resulting layer thickness was approximately 70 nm.

The substrate with the coated polymer layer was exposed to linearly polarized UV light (LPUV) at an incident angle of 40° relative to the normal to the substrate surface. The polarization plane was in the plane between the substrate normal and the propagation direction of the light. The applied exposure dose was 48 mJ/cm ² .

After LPUV exposure, the cell was assembled with two substrates, with the exposed polymer layer facing the inner side of the cell. The substrates were adjusted relative to each other so that the induced alignment directions were parallel to each other (corresponding to an antiparallel rubbed configuration in the case of alignment by rubbing). The cell was filled with MLC6610 liquid crystal (Merck KGA) with negative dielectric anisotropy using a vacuum method. The liquid crystal in this cell exhibited a well-defined homeotropic orientation with a tilt angle of 87.86° measured using the crystal rotation method.

Example 16:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 2 having side substitutions in different directions was used instead of polyamic acid 1, and a spinning speed of 1250 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 88.40°.

Example 17:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 3 was used and a spinning speed of 1600 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 88.96°.

Example 18:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 4 was used and a spinning speed of 1750 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 88.34°.

This indicates that the pretilt angle can be adjusted by maintaining the same alignment layer coating steps using the liquid crystal cell processing conditions. The structure of the polymer can be modified by different pendant substitutions on the polymer.

Example 19:

Preparation of 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol:

3.6 g (10.83 mmol) of 4,4'-dinitro-1,1'-biphenyl-2,2'-dicarboxylic acid was dissolved in 25 ml of tetrahydrofuran and added dropwise over 1 hour to 65 ml (65.02 mmol) of a 1.0 M solution of a borane-tetrahydrofuran complex in tetrahydrofuran. After 19 hours at 25°C, 50 ml of water were gradually added. After 1 hour, the solution was acidified to pH 1-2 with 10 ml of 1N HCl solution and stirred for 30 minutes. The reaction mixture was then partitioned between ethyl acetate and water; the organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The residue, 4.2 g of 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol, was used as a white powder without further purification.

Example 20/Preparation of 2-(2,4-dinitrophenyl)propane-1,3-diol:

20 g (106.5 mmol) of 2,4-dinitrotoluene was dissolved in 280 mL of NMP. 7.6 g (255.6 mmol) of paraformaldehyde was added to the brown solution. 597 mg (5.32 mmol) of potassium tetrabutoxide was added to the suspension. The resulting solution was stirred at room temperature overnight. The mixture was poured onto 200 mL of ice and neutralized with 2 mL of 25% HCl. The reaction mixture was then partitioned between ethyl acetate and water; the organic phase was repeatedly washed with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. The solution was precipitated at room temperature by adding 150 mL of heptane. The product was filtered and dried under vacuum at room temperature. The product was isolated as 16.15 g of a pale yellow product.

Example 21/Compound 21, namely 2-fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid 4-((1E)-3-{[2'- ({[(2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)propan-2-yl]oxy)methyl Preparation of [4,4'-dinitro-1,1'-biphenyl-2-yl]-[ ...

8.48 g (27.9 mmol) of 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol, 23.0 g (55.7 mmol) of compound 5, and 170 mg (1.4 mmol) of 4-dimethylaminopyridine were dissolved in 100 mL of dichloromethane. 8.64 g (55.7 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) were added at 0°C. The solution was stirred at 0°C for 1 hour and at room temperature overnight. After 22 hours at room temperature, the reaction mixture was partitioned between dichloromethane and water. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was chromatographed on 200 g of silica gel using toluene:ethyl acetate 95:5 as eluent and crystallized from an ethyl acetate:hexane mixture to yield 21 g (71%) of compound 21 as colorless crystals.

Example 22/Compound 22

Preparation of 4-[(1E)-3-(2-(2,4-dinitrophenyl)-3-{[(2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)prop-2-yl]oxy}propoxy)-3-oxoprop-1-enyl]phenyl 4-(4,4,4-trifluorobutoxy)-2-fluorobenzoate:

Dissolve 6.75 g (27.9 mmol) of 2-(2,4-dinitrophenyl)-propane-1,3-diol, 23.0 g (55.7 mmol) of compound 5, and 170 mg (1.4 mmol) of 4-dimethylaminopyridine in 100 mL of dichloromethane. Add 8.64 g (55.7 mmol) of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC hydrochloride) at 0°C. Stir the solution at 0°C for 1 hour and at room temperature overnight. After 22 hours at room temperature, partition the reaction mixture between dichloromethane and water. Wash the organic phase repeatedly with water, dry over sodium sulfate, filter, and concentrate under reduced pressure.

The residue was chromatographed on 200 g of silica gel using toluene:ethyl acetate 95:5 as eluent and crystallized from ethyl acetate:hexane mixture to yield 21.3 g (74%) of compound 22 as colorless crystals.

Example 23/Compound 23, namely 2-fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid 4-((1E)-3-{[4,4'-difluorobutyloxy)benzoic acid amino-2'-({[(2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)propan-2-yl] Preparation of 1,1'-biphenyl-2-yl]- ...

9.15 g (8.38 mmol) of compound 21 were dissolved in a mixture of 54 mL of N,N-dimethylformamide and 6 mL of water. 13.9 g (51.4 mmol) of ferric chloride hexahydrate were added. 5.60 g (85.7 mmol) of zinc powder were added in portions over 60 minutes. The mixture was allowed to react for 2 hours. The reaction mixture was partitioned between ethyl acetate and water and filtered. The organic phase was washed repeatedly with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was filtered over 200 g of silica gel using a mixture of toluene:ethyl acetate 1:3 as eluent and crystallized from an ethyl acetate:hexane mixture to produce 6.05 g of compound 23 as colorless crystals.

Example 24/Compound 24, i.e., Preparation of 4-[(1E)-3-(2-(2,4-diaminophenyl )-3-{[(2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)prop-2- yl]oxy}propoxy)-3-oxoprop-1-enyl]phenyl 4-(4,4,4-trifluorobutoxy)-2-fluorobenzoate :

8.63g (8.38mmol) of compound 22 is dissolved in a mixture of 54mL N,N-dimethylformamide and 6mL water. 13.9g (51.4mmol) of ferric chloride hexahydrate is added. 5.60g (85.7mmol) of zinc powder is added in batches over 60 minutes. The mixture is reacted for 2 hours. The reaction mixture is layered and filtered between ethyl acetate and water. The organic phase is repeatedly washed with water, dried over sodium sulfate, filtered under reduced pressure and concentrated. The residue is filtered on 200g of silica gel, using toluene: ethyl acetate 1:3 as eluent, and from ethyl acetate: hexane mixture crystallization, producing 6.50g of compound 24 as colorless crystals.

Example 25:

0.277 g (1.24 mmol) of 2,3,5-tricarboxycyclopentylethane-1,2:3,4-dianhydride was added to a solution of 1.20 g (1.24 mmol) of compound 24 in 3.51 mL of NMP. The mixture was then stirred at 0°C for 2 hours. The mixture was then allowed to react at room temperature for 21 hours. The polymer mixture was diluted with 25 mL of THF, precipitated in 800 mL of water, and dried under vacuum at room temperature to produce 1.1 g of polyamic acid 25 in the form of a white powder: [h] = 0.19 dl/g

Example 26:

Similar to Example 25, the following diamines and 2,3,5-tricarboxycyclopentylethane-1,2:3,4-dianhydride were used to prepare polyamic acid.

Compound 23

Produces polyamic acid 26 as a white powder; [η] = 0.48 dL/g

Example 27

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 25 was used and a spinning speed of 1500 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as in Example 15 and was 88.05°.

Example 28/Preparation of Compound 28, 3-methoxy-4-(4,4,4-trifluorobutoxy)benzoic acid

This compound was prepared according to the method described in Example 7 of Compound 7, except that bromopentane was replaced by 4-iodo-1,1,1-trifluorobutane.

Example 29/Compound 29, 4-formylphenyl 3-methoxy-4-(4,4,4-trifluorobutoxy)benzoate preparation

This compound was prepared according to the method described in Example 3 of Compound 3, except that Compound 2 was replaced by Compound 28.

Example 30/Compound 30, namely (2E)-3-(4-{[3-methoxy-4-(4,4,4-trifluorobutoxy)benzoyl] Preparation of 2-(4-(2 ...oxy}phenyl)prop-2-enoic acid)

This compound was prepared according to the method described in Example 4 of Compound 4, with the proviso that Compound 3 was replaced by Compound 29.

Example 31/Compound 31, namely 3-methoxy-4-(4,4,4-trifluorobutoxy)benzoic acid 4-[(1E)-3-({6- Preparation of [(3,5-dinitrobenzoyl)oxy]hexyl}oxy)-3-oxoprop-1-enyl]phenyl ester

This compound was prepared according to the method described in Example 5 of Compound 5B, with the proviso that Compound 4B was replaced by Compound 30.

Example 32/Compound 32, namely 3-methoxy-4-(4,4,4-trifluorobutoxy)benzoic acid 4-[(1E)-3-({6- Preparation of [(3,5-diaminobenzoyl)oxy]hexyl}oxy)-3-oxoprop-1-enyl]phenyl ester

This compound was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5B was replaced by Compound 31.

Example 33/Preparation of Compound 33, 3,4-bis[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid

This compound was prepared according to the method described in Example 7 of Compound 7, with the proviso that bromopentane was replaced by 5-iodo-1,1,1,2,2-pentafluoropentane and methyl vanillate was replaced by ethyl 3,4-dihydroxybenzoate.

Example 34/Compound 34, namely 3,4-bis[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid 4-formylphenyl Preparation of esters

This compound was prepared according to the method described in Example 3 of Compound 3, with the proviso that Compound 2 was replaced by Compound 33.

Example 35/Compound 35, namely (2E)-3-[4-({3,4-bis[(4,4,5,5,5-pentafluoropentyl)oxy)benzoyl Preparation of 1,2-dimethyl}oxy)phenyl]prop-2-enoic acid

This compound was prepared according to the method described in Example 4 of Compound 4, with the proviso that Compound 3 was replaced by Compound 34.

Example 36/Compound 36, namely 3,4-bis[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid 4-{(1E)-3- Preparation of [2-(2,4-dinitrophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl ester

This compound was prepared according to the method described in Example 5 of Compound 5, with the proviso that Compound 4 was replaced by Compound 35.

Example 37/Compound 37, namely 3,4-bis[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid 4-{(1E)-3- Preparation of [2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl)phenyl ester

This compound was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 36.

Example 38/Preparation of Compound 38, 2-fluoro-4-[(4,4,5,5,5-pentafluoropentyl)oxy]benzonitrile

This compound was prepared according to the method described in Example 1 of Compound 1, with the proviso that 4-iodo-1,1,1-trifluorobutane was replaced by 5-iodo-1,1,1,2,2-pentafluoropentane.

Example 39/Preparation of Compound 39, 2-fluoro-4-[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid

This compound was prepared according to the method described in Example 2 of Compound 2, with the proviso that Compound 1 was replaced by Compound 38.

Example 40/Compound 40, namely 2-fluoro-4-[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid 4-formylbenzene Preparation of esters

This compound was prepared according to the method described in Example 3 of Compound 3, with the proviso that Compound 2 was replaced by Compound 39.

Example 41/Compound 41, namely (2E)-3-4-({2-fluoro-4-[(4,4,5,5,5-pentafluoropentyl)oxy]benzoyl Preparation of 1,2-dimethyl}oxy)phenyl]prop-2-enoic acid

This compound was prepared according to the method described in Example 4 of Compound 4, with the proviso that Compound 3 was substituted for Compound 40.

Example 42/Compound 42, namely 2-fluoro-4-[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid 4-{(1E)-3- Preparation of [2-(2,4-dinitrophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl ester

This compound was prepared according to the method described in Example 5 of Compound 5, with the proviso that Compound 4 was replaced by Compound 41.

Example 43/Compound 43, namely 2-fluoro-4-[(4,4,5,5,5-pentafluoropentyl)oxy]benzoic acid 4-{(1E)-3- Preparation of [2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl)phenyl ester

This compound was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 42.

Example 44/Preparation of Compound 44, methyl 2-fluoro-4-(4,4,4-trifluorobutoxy)benzoate

3.0 g (11.3 mmol) of 2-fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid was refluxed in 40 mL of methanol and 2 drops of sulfuric acid for 22 hours. The solvent was evaporated under vacuum. The crude product was used without further purification.

Example 45/Preparation of Compound 45, [2-fluoro-4-(4,4,4-trifluorobutoxy)phenyl]methanol

3.13g (11.2mmol) of compound 44 in 40mL THF was cooled to 0°C. To this solution was added 8.8mL of LiAlH4THF solution. After 3 hours, the solution was quenched by adding 20mL of HCl 1N. The product was extracted with AcOEt and washed with 200mL of water. The organic phase was dried over sodium sulfate and desolvated under vacuum to obtain 2.32g of compound 45 as an orange oil.

Example 46/Preparation of Compound 46, 1-(bromomethyl)-2-fluoro-4-(4,4,4-trifluorobutoxy)benzene

2.00g (7.93mmol) compound 45 and 3.42g (10.31mmol) CBr4 are dissolved in 20mL THF.To this solution, 2.70g (10.31mmol) triphenylphosphine is added.After 1 hour, mixture is filtered on silica gel plug, and with the mixture elution of AcOEt/ hexane 1/1.Under vacuum, remove excess solvent, obtain 2.28g compound 46 as colorless oil.

Example 47/ Preparation of Compound 47, 4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzyl]oxy}benzaldehyde Preparation

0.66 g (2.09 mmol) of compound 46, 0.32 g (2.30 mmol) of K ₂ CO ₃ , and 0.25 g (2.30 mmol) of 4-hydroxybenzaldehyde were mixed in 10 mL of NMP. The mixture was heated to 65° C. for one hour. The solution was poured into 100 mL of 0.1 N HCl. The solid was filtered and dried under vacuum to give compound 47.

Example 48/Compound 48, namely (2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzyl]oxy}benzene Preparation of 2-amino-3-amino-1-propenoic acid

This compound was prepared according to the method described in Example 4 of Compound 4, with the proviso that Compound 3 was replaced by Compound 47.

Example 49/Compound 49, namely (2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzyl]oxy}benzene Preparation of 2-(2,4-dinitrophenyl)ethyl propan-2-ate

This compound was prepared according to the method described in Example 5 of Compound 5, with the proviso that Compound 4 was replaced by Compound 48.

Example 50/Compound 50, namely (2E)-3-(4-{[2-fluoro-4-(4,4,4-trifluorobutoxy)benzyl]oxy}benzene Preparation of 2-(2,4-diaminophenyl)ethyl propan-2-ate

This compound was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 49.

Example 51/Preparation of Compound 51, 1,2-difluoro-3-(4,4,4-trifluorobutoxy)benzene

This compound was prepared according to the method described in Example 1 of Compound 1, with the proviso that 3-fluoro-4-hydroxybenzonitrile was replaced by 2,3-difluorophenol.

Example 52/Preparation of Compound 52, 2,3-difluoro-4-(4,4,4-trifluorobutoxy)phenylboronic acid

5.0g (20.8mmol) compound 51 is dissolved in 58mL THF and cooled to-78 ℃.To this solution, 7.71mL (20.8mmol) BuLi solution in hexane is added dropwise.After 3 hours, 2.84mL (24.98mmol) trimethyl borate in 20mL THF is added to the previous solution.After adding, this solution is stirred at room temperature overnight.By adding 20ml HCl 1N, the mixture is quenched.The gained emulsion is processed by adding 10mL concentrated HCl.The mixture is stirred 2 hours.Extract the organic phase with ethyl acetate, wash with water, and use dried over sodium sulfate.Desolventize under vacuum to obtain 5.3g compound 52 as a brown solid.

Example 53/Compound 53, namely 2',3'-difluoro-4'-(4,4,4-trifluorobutoxy)-1,1'-biphenyl-4-carbaldehyde Preparation

5.3 g (18.66 mmol) of compound 52, 3.4 g (18366 mmol) of 4-bromobenzaldehyde, and 862 mg (0.74 mmol) of tetrakis(triphenylphosphine)palladium were mixed in 90 mL of toluene. The mixture was degassed and purged with nitrogen. The reaction was heated to 50° C., and 90 mL of _{2M Na₂CO₃} was slowly added. The reaction was heated to 90° C. and stirred for 2 days. After cooling to room temperature, the mixture was quenched with 50 mL of 25% HCl. The organic phase was extracted with ethyl acetate and dried over sodium sulfate. Excess solvent was removed under vacuum. Product 53 was purified by flash chromatography on silica gel using a mixture of toluene/AcOEt 98/2.

Example 54/Compound 54, namely (2E)-3-[2',3'-difluoro-4'-(4,4,4-trifluorobutoxy)-1,1'- Preparation of [4-phenyl]prop-2-enoic acid

This compound was prepared according to the method described in Example 4 of Compound 4, with the proviso that Compound 3 was replaced by Compound 53.

Example 55/Compound 55, namely (2E)-3-[2',3'-difluoro-4'-(4,4,4-trifluorobutoxy)-1,1'- Preparation of 2-(2,4-dinitrophenyl)ethyl]phenyl-4-yl]propan-2-oate

This compound was prepared according to the method described in Example 5 of Compound 5, with the proviso that Compound 4 was replaced by Compound 54.

Example 56/Compound 56, namely (2E)-3-[2',3'-difluoro-4'-(4,4,4-trifluorobutoxy)-1,1'- Preparation of 2-(2,4-diaminophenyl)ethyl]phenyl-4-ylpropane-2-olate

This compound was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 55.

Example 57/Compound 57, namely 2-fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid 4-{(1E)-3-[(3,5-difluorobutyloxy)benzoic acid Preparation of [3-nitrobenzyl]oxy]-3-oxoprop-1-enyl)phenyl ester

This compound was prepared according to the method described in Example 5 of Compound 5, with the proviso that the compound 2,4-dinitrophenylethanol was replaced by 3,5-dinitrobenzyl alcohol.

Example 58/Compound 58, namely 2-fluoro-4-(4,4,4-trifluorobutoxy)benzoic acid 4-{(1E)-3-[(3,5-difluorobutyloxy)benzoic acid Preparation of [aminobenzyl]oxy]-3-oxoprop-1-enyl]phenyl ester

This compound was prepared according to the method described in Example 6 of Compound 6, with the proviso that Compound 5 was replaced by Compound 57.

Example 59:

Similar to Example 10, the following diamines and 2,3,5-tricarboxycyclopentylethane-1,2:3,4-dianhydride were used to prepare polyamic acid .

Compound 37

Produces polyamic acid 60 as a white powder; [η] = 0.24 dL/g

Compound 43

Produces polyamic acid 61 as a white powder; [η] = 0.28 dL/g

Compound 50

Produces polyamic acid 62 as a white powder; [η] = 0.25 dL/g

Compound 56

Produces polyamic acid 63 as a white powder; [η] = 0.21 dL/g

Compound 58

Produces polyamic acid 64 as a white powder; [η] = 0.32 dL/g

Example 60:

Similar to Example 10, the following diamines and 1,2,3,4-cyclobutanetetracarboxylic dianhydride were used for the preparation of polyamic acid.

Compound 32

Produces polyamic acid 59 as a white powder; [η] = 0.38 dL/g

Example 61:

Similar to Example 10, the following mixture of diamines and 1,2,3,4-cyclobutanetetracarboxylic dianhydride were used to prepare polyamic acid.

A mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and compound 6 and 4-{(1E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxoprop-1-enyl}phenyl 4-(4,4,4-trifluorobutoxy)benzoate 50:50 (molar ratio) yielded polyamic acid 65 as a white powder; [η] = 0.64 dL/g

^1H NMR 300MHz DMSO d6:

12.51(s, 2H), 10.19(s, 1H), 9.59(s, 1H), 8.08-7.61(m, 6H), 7.43-6.94(m, 7H), 6.65-6.59( m, 1H), 4.30 (s, 2H), 4.16 (s, 2H), 3.83-3.58 (m, 4H), 2.95 (s, 2H), 2.39 (m, 2H), 1.96 (m, 2H).

Example 62:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 25 was used and a spinning speed of 1200 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 88.15°.

Example 63:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 26 was used and a spinning speed of 1400 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 88.60°.

Example 64:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 59 was used and a spinning speed of 1600 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 89.33°.

Example 65:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 60 was used and a spinning speed of 1900 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 87.44°.

Example 66:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 61 was used and a spinning speed of 1800 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 88.52°.

Example 67:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 62 was used and a spinning speed of 1200 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 77.2°.

Example 68:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 63 was used and a spinning speed of 1200 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 89.61°.

Example 69:

Another liquid crystal cell was prepared in the same manner as described in Example 15, except that polyamic acid 64 was used and a spinning speed of 1600 rpm for 30 seconds was used.

The pretilt angle was measured in the same manner as described in Example 15 and was 87.84°.

Claims (7)

1. A photoalignment material comprising a polymer having at least one side-substituted moiety represented by formula (II) on its side chains. in B is an unsubstituted or substituted 1,4-phenylene, wherein the substituent is selected from _C1 - _C6 alkyl, _C1 - _C6 alkoxy, chlorine, fluorine or nitrile; Z represents -COO-, -OCO-, _-OCH2- , _-CH2O- , or a single bond. ^R1 represents fluorine. ^R2 and ^R3 are hydrogen. U represents a _C1 - _C16 alkyl group that is hydrogen-containing or straight-chain or branched, unsubstituted, or substituted at least once with a nitrile, ether, ester, siloxane, amide, or amine, and X is -O(CO)-, -(CO)O-. 2. A photoalignment material comprising a polymer having at least one side-substituted moiety represented by formula (III) on its side chains, in Z represents -COO-, -OCO-, _-OCH2- , _-CH2O- , or a single bond. ^R1 represents fluorine. U represents a _C1 - _C16 alkyl group that is hydrogen-containing or straight-chain or branched, unsubstituted, or substituted at least once with a nitrile, ether, ester, siloxane, amide, or amine. X is -O(CO)-, -(CO)O-. R1 ^′ is fluorine, and R ^1" indicates hydrogen, fluorine, or chlorine. 3. The photoalignment material according to claim 1 or 2, comprising a polymer having at least one side-substituted portion represented by formula (II) or (III) on the bicolor side chain. 4. A composition comprising a photoaligning material having at least one side-substituted portion on a side chain, represented by formula (II) of any one of claims 1 and 3, or formula (III) of claim 2. 5. A method for preparing an alignment layer, comprising coating a carrier with the photoalignment material of any one of claims 1-3 or the composition of claim 4, and treating it with alignment light. 6. An alignment layer comprising at least one photoaligning material having at least one side-substituted portion on a side chain represented by formula (II) of any one of claims 1 and 3, or formula (III) of claim 2, or the composition of claim 4. 7. Optical and optoelectronic non-structural or structural constituent elements comprising at least one alignment layer according to claim 6, or comprising at least one photoalignment material according to any one of claims 1-3, or the composition according to claim 4.