KR100694936B1 - Polymerizable mesogenic tolanes - Google Patents

Abstract

The present invention relates to a polymerizable tolan of Formula 1, a polymerizable liquid crystal composition comprising at least one compound of Formula 1, a linear or crosslinked liquid crystal polymer obtainable from these compounds and compositions, and a compound of Formula 1, a polymerizable composition and Optical elements such as polarizers, retardation and reinforcement films, alignment layers, color filters or holographic elements, of polymers obtainable from the polymer; Liquid crystal displays such as PDLC, polymer gel or polymer stabilized cholesteric texture (PSCT) displays; Adhesives, synthetic resins having anisotropic mechanical properties, cosmetics, diagnostics or liquid crystal pigments; For decoration and protection; And non-linear optics or optical information storage:

Where

또는 CH₂=CH-페닐-(O)_k-이고(여기서, W는 H, CH₃ 또는 Cl이고, k는 0 또는 1이다),P is CH ₂ = CW-COO-, WCH = CH-O-,

Or CH ₂ ═CH-phenyl- (O) _k −, where W is H, CH ₃ or Cl, and k is 0 or 1,

Sp is a spacer group having 1 to 25 carbon atoms,

X is -O-, -S-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O -, -SCH _2- , -CH ₂ S-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, -C≡C- or a single bond,

n is 0 or 1,

Z ¹ and Z ² are each independently -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -CH = CH-COO-,- OCO-CH = CH-, -C≡C- or a single bond,

A ¹ and A ² are each independently 1,4-phenylene, wherein one or more CH groups may be substituted by N, 1,4-cyclohexylene, wherein one or two non-contiguous CH ₂ Groups may be substituted by O and / or S), 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) octylene, piperidine-1,4-diyl, naphthalene -2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, all such groups being unsubstituted, F, Cl, CN, Mono- or polysubstituted by OH, NO ₂ or an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, wherein one or more H atoms may be substituted by F or Cl,

m1 and m2 are each independently 0, 1 or 2, and the sum of m1 and m2 is less than 3,

L ¹ and L ² are each independently F, Cl, CN, OH, NO ₂ or an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, wherein one or more H atoms may be substituted by F or Cl ego,

r are each independently 0, 1, 2, 3 or 4,

R is H, CN, halogen, or a straight or branched chain alkyl radical having 25 or less carbon atoms, which may be unsubstituted or mono- or polysubstituted by halogen or CN, wherein at least one non-contiguous CH ₂ group is Independently of each other in the case -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-,- CO-S- or -C≡C- may be substituted so that the oxygen atoms are not directly connected to each other), or alternatively R represents P- (Sp-X) _n- ,

이고, m1과 m2의 합이 0인 경우, R은 P-(Sp-X)_n-이고/이거나 하나 이상의 r은 0이 아니고,A) P is CH ₂ = CW-COO- or

When the sum of m1 and m2 is zero, R is P- (Sp-X) _n -and / or one or more r is not zero,

b) P is CH ₂ = CW-COO-, ^one of-(A ¹ -Z ¹ ) _m1 -and-(A ² -Z ² ) _m2 -is substituted or unsubstituted phenylene and the other is a single bond When R is P- (Sp-X) _n and / or n is 1,

c) When the sum of m1 and m2 is 2, A ¹ and A ² are not cyclohexylene.

Description

POLYMERIZABLE MESOGENIC TOLANES

The present invention relates to a polymerizable liquid crystal composition comprising a polymerizable mesogenic tolan, a polymerizable mesogenic tolan, a polymerizable mesogenic tolan and a linear or crosslinked liquid crystal polymer obtainable from a composition comprising the same, and a polymerizable mesogenic tolan and a polymerization. Optical compositions, liquid crystal displays, adhesives, synthetic resins having anisotropic mechanical properties, cosmetics, diagnostics, liquid crystal pigments, decorative and protective, nonlinear optics and optical information storage of polymers and polymers obtained therefrom.

Polymerizable mesogenic compounds, also known as reactive mesogenic compounds, have been described in the prior art for various purposes. For example, they can be aligned in the liquid crystal phase and then polymerized in situ to give a linear or crosslinked liquid crystal polymer film having a high quality constant orientation. Such films include, for example, polarizing filters as described in European Patent 0 397 263, broadband circular polarizers as described in European Patent 0 606 940 and WO 97/35219, or International Publications. It can be used as an optical element such as a reinforcing or retarding film as described in WO 98/00475, WO 98/04651 or WO 98/12584.

However, polymerizable mesogenic compounds described in the prior art often exhibit a liquid crystalline phase or only a mesophase aspect at a narrow temperature range. In addition, polymerizable mesogenic compounds of the prior art often exhibit only low or moderate values of birefringence.

When producing an oriented liquid crystal polymer film for use as described above, it is particularly preferred that the available polymerizable compositions exhibit a nematic liquid crystal phase at room temperature so that the alignment and polymerization of the composition can be carried out at low temperatures. . For this purpose, it is advantageous for even a single polymerizable component to exhibit a wide liquid crystal phase.

Therefore, there is a need for a polymerizable mesogenic compound having a wide liquid crystal phase and a high birefringence, which can be used in the preparation of an oriented liquid crystal polymer film for optical applications.

In addition, given the wide range of uses for the polymerizable mesogenic compounds, it is desirable for the skilled person to employ additional compounds of the type that are easy to synthesize and which meet the various requirements as described above.

It is an object of the present invention to provide polymerizable mesogenic compounds with advantageous properties to expand the scope of reactive mesogenic compounds available to the skilled person. Other objects of the present invention will immediately become apparent to those skilled in the art from the following detailed description.

It has been found that this object can be obtained by providing a polymerizable mesogenic tolan according to the present invention.

Polymerizable mesogenic compounds comprising a tolan group are disclosed in International Publication Nos. 98/52905, European Patent No. 0 659 865, Japanese Patent No. 11-147853, Japanese Patent No. 11-080090, Japanese Patent No. 08-231958, Japanese Patent No. 07-109351, and Japanese Patent No. 07-017910.

The term reactive or polymerizable mesogenic compounds, used before and after, includes rod-shaped, plate-shaped or discotic mesogenic groups, ie compounds having a group having the ability to induce mesophase patterns. These compounds do not need to exhibit mesophase behavior on their own. Such compounds may also exhibit mesophase behavior only in admixture with other compounds or when polymerizable mesogenic compounds or mixtures comprising the same are polymerized.

One object of the present invention is a polymerizable mesogenic tolan of formula (I):

Formula 1

Where                     

또는 CH₂=CH-페닐-(O)_k-이고(여기서, W는 H, CH₃ 또는 Cl이고, k는 0 또는 1이다),P is CH ₂ = CW-COO-, WCH = CH-O-,

Or CH ₂ ═CH-phenyl- (O) _k −, where W is H, CH ₃ or Cl, and k is 0 or 1,

Sp is a spacer group having 1 to 25 carbon atoms,

X is -O-, -S-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O -, -SCH _2- , -CH ₂ S-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, -C≡C- or a single bond,

n is 0 or 1,

Z ¹ and Z ² are each independently -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -CH = CH-COO-,- OCO-CH = CH-, -C≡C- or a single bond,

A ¹ and A ² are each independently 1,4-phenylene, wherein one or more CH groups may be substituted by N, 1,4-cyclohexylene, wherein one or two non-contiguous CH ₂ Groups may be substituted by O and / or S), 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) octylene, piperidine-1,4-diyl, naphthalene -2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, all such groups being unsubstituted, F, Cl, OH, Mono- or polysubstituted by CN, NO ₂ or an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, wherein one or more H atoms may be substituted by F or Cl,

m1 and m2 are each independently 0, 1 or 2, and the sum of m1 and m2 is less than 3,

L ¹ and L ² are each independently F, Cl, CN, OH, NO ₂ or an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, wherein one or more H atoms may be substituted by F or Cl ego,

r are each independently 0, 1, 2, 3 or 4,

R is H, CN, halogen, or a straight or branched chain alkyl radical having 25 or less carbon atoms, which may be unsubstituted or mono- or polysubstituted by halogen or CN, wherein at least one non-contiguous CH ₂ group is Independently of each other in the case -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-,- CO-S- or -C≡C- may be substituted so that the oxygen atoms are not directly connected to each other), or alternatively R represents P- (Sp-X) _n- ,

이고, m1과 m2의 합이 0인 경우, R은 P-(Sp-X)_n-이고/이거나 하나 이상의 r은 0이 아니고,A) P is CH ₂ = CW-COO- or

When the sum of m1 and m2 is zero, R is P- (Sp-X) _n -and / or one or more r is not zero,

b) P is CH ₂ = CW-COO-, ^one of-(A ¹ -Z ¹ ) _m1 -and-(A ² -Z ² ) _m2 -is substituted or unsubstituted phenylene and the other is a single bond When R is P- (Sp-X) _n and / or n is 1,

c) When the sum of m1 and m2 is 2, A ¹ and A ² are not cyclohexylene.

Another object of the invention relates to a polymerizable liquid crystal composition comprising at least two polymerizable components, at least one of which is a compound of formula (1).

Another object of the present invention is a linear or crosslinked polymer obtained by polymerizing a polymerizable composition comprising at least one compound of formula (1) or at least one compound of formula (1).

Another object of the present invention is to provide an optical device, such as a polarizer, an optical retardation or reinforcement film, an alignment layer, a color filter or a holographic device, of a compound of formula 1 or a polymerizable composition or polymer obtained therefrom; Liquid crystal displays such as PDLC, polymer gel or polymer stabilized cholesteric texture (PSCT) displays; Adhesives, synthetic resins having anisotropic mechanical properties, cosmetics, diagnostics, liquid crystal pigments; For decoration and protection; And for nonlinear optical or optical information storage.

Particularly preferred compounds of formula 1 are

A compound in which the sum of m1 and m2 is 1 or more;

At least one of A ¹ and A ² is an aryl group, preferably wherein the sum of m 1 and m 2 is 1;

A compound in which one of m1 and m2 is 1 and the other is 0,
A compound wherein m1 is 1 and m2 is 0,

A compound wherein at least one of Z ¹ and Z ² is -COO- or -OCO-,

R is a compound having one of the meanings provided for P- (Sp-X) _n ,

R is a halogen, cyano, or optionally fluorinated, non-chiral or chiral alkyl or alkoxy group having 1 to 15 carbon atoms,

N is 1 compound,

Sp is a compound which is alkylene having 1 to 12 carbon atoms,

X is a compound which is -O- or a single bond.

Particularly preferred compounds of formula (I) wherein P is CH ₂ = CW-COO- are those wherein n is 1.

Among the compounds of the formula (1), wherein the sum of m1 and m2 is 1 or 2, a compound wherein n is 1, one or both of Z ¹ and Z ² are ester groups, and R is P- (Sp-X) _n- Particularly preferred.

Among the compounds of the formula (1) wherein the sum of m1 and m2 is 2, particularly those compounds in which A ¹ and A ² are substituted or unsubstituted 1,4-phenylene, wherein one or more CH groups may be substituted by N desirable.

Of the polymerizable mesogenic compounds of the formula ( ¹ ), compounds in which-(A ¹ -Z ¹ ) _m1 -and-(Z ² -A ² ) _m2 -each independently represent a group having one or two six-membered rings are particularly preferred. Do.

The groups of-(A ¹ -Z ¹ ) _m1 -and-(Z ² -A ² ) _m2 -may be the same or different. Particularly preferred compounds are compounds in which-(A ¹ -Z ¹ ) _m1 -and-(Z ² -A ² ) _m2 -are different.

Preferred partial formulas for the groups-(A ¹ -Z ¹ ) _m1 -and-(Z ² -A ² ) _m2 -are listed below. For simplicity, in the group Phe is 1,4-phenylene and PheL is a 1,4-phenylene group substituted with 1 to 4 groups L, where L is F, Cl, CN, OH, NO ₂ Or an optionally fluorinated alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, and Cyc is 1,4-cyclohexylene. Preferred-formula through the group to the list, as well as part of the formula 2-1 to 2-9 including its mirror image, in which the radical ^{Z - (A 1 -Z 1)} m1 - and - (Z ² -A ²⁾ _m2 Is connected to the tolan group of 1.

-Phe-Z- 2-1 -Cyc-Z- 2-2 -PheL-Z- 2-3 -Phe-Z-Phe-Z- 2-4 -Phe-Z-Cyc-Z- 2-5 -Cyc-Z-Cyc-Z- 2-6 -PheL-Z-Phe-Z-- 2-7 -PheL-Z-Cyc-Z- 2-8 -PheL-Z-PheL-Z- 2-9

Particular preference is given to partial formulas 2-1, 2-3, 2-7 and 2-8.

In this preferred group, Z has the meaning of Z ¹ as shown in formula (1). Preferably Z is -COO-, -OCO-, -CH ₂ CH _2- , -C≡C- or a single bond.

Very preferably _{^{- (A 1 -Z 1) m1}} - and _{^{- (Z 2 -A 2) m2}} - are, independently of each other to be selected from the general formula 2a to 2f and their mirror images, which tolran of formula I via a radical Z Is connected to:

Where

Z and L have the meanings provided above and r is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

는 매우 바람직하게는 또는

, 추가로

를 나타내고, 여기서 L은 각각 독립적으로 상기 제공된 의미중 하나를 갖는다.In this preferred formula

Very preferably or

, Add to

Wherein L each independently has one of the meanings provided above.

Partial formulas 2a, 2c, 2f, 2g and 2h are preferred, in particular partial formulas 2a, 2d and 2f.

(여기서, r은 1이다)를 포함하는 화학식 1의 화합물이 특히 바람직하다.One or more groups

Particularly preferred are compounds of formula 1, wherein r is 1.

(여기서, r은 1이다) 및/또는 하나 이상의 기

(여기서, r은 2이다)를 포함하는 화학식 1의 화합물이 추가로 바람직하다.More than one flag

(Where r is 1) and / or one or more groups

Further preferred are compounds of formula 1, wherein r is 2.

L is preferably F, Cl, CN, OH, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , in particular F, Cl, CN, CH ₃ , C ₂ H ₅ , OCH ₃ , COCH ₃ and OCF ₃ , most preferably F, Cl, CH ₃ , OCH ₃ and COCH ₃ .

L ¹ and L ² in Formula 1 are preferably, independently of each other, F, Cl, CN, OH, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ or OC ₂ F ₅ , in particular F, Cl, OCH ₃ or OCF ₃ , most preferably F, Cl or OCH ₃ . r is preferably 0, 1 or 2, most preferably 0 or 1.

If R in the formula (1) is an alkyl or alkoxy radical, wherein the terminal CH ₂ group is substituted by -O-, it may be straight or branched. It is preferably straight-chain and has 2, 3, 4, 5, 6, 7 or 8 carbon atoms, so for example ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, Propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, further methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, nonoxy, decock City, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

Oxaalkyl, where one CH ₂ group is substituted by -O-, is preferably, for example, straight-chain 2-oxapropyl (= methoxymethyl), 2-(= ethoxymethyl) or 3 Oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxhexyl, 2-, 3-, 4-, 5- or 6 -Oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxactyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2- , 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadedecyl.

In the compound of formula 1, R may be a non-chiral or chiral group. In the case of chiral groups, it is preferred to be selected according to formula (3):

Where

X ¹ is -O-, -S-, -CO-, -COO-, -OCO-, -OCOO- or a single bond,

Q ¹ is an alkylene or alkylene-oxy group or single bond having 1 to 10 carbon atoms,

Q ² is an unsubstituted, mono- or polysubstituted alkyl or alkoxy group having 1 to 10 carbon atoms, wherein at least one non-adjacent CH ₂ group is independently of each other at each occurrence of -C≡. C-, -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO- or -CO- S- may be substituted in such a way that the oxygen atoms are not directly connected to each other,

Q ³ is a halogen, cyano group or alkyl or alkoxy group having 1 to 4 carbon atoms different from Q ² .

When Q ¹ in the formula (3) is an alkylene-oxy group, the O atom is preferably adjacent to the chiral C atom.

Preferred chiral groups R are, for example, 2-butyl (= 1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-octyl, in particular 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3 -Oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxyoctoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyl Oxycarbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2-chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4- Methylvaleryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl- 2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy.

In addition, compounds of formula (1) containing branched groups R that are not chiral may sometimes be important due to, for example, a decrease in crystallization tendency. Branched groups of this type generally do not contain one or more branched chains. Preferred non-chiral branched groups are isopropyl, isobutyl (= methylpropyl), isopentyl (= 3-methylbutyl), isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.                     

Very preferably R of formula 1 is halogen, cyano or optionally fluorinated chiral or chiral alkyl or alkoxy group having 1 to 15 carbon atoms.

Another preferred embodiment of the invention relates to compounds of formula 1, _wherein R represents P- (Sp-X) _n- .

P in formula 1 is preferably an acrylate group, methacrylate group, vinyl or vinyloxy group, epoxy group, styrene group or propenyl ether group, in particular an acrylate, methacrylate, vinyl or epoxy group.

As for the spacer group Sp in Formula 1, any group known for this purpose to those skilled in the art can be used. The spacer group Sp is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, in particular 1 to 12 carbon atoms, and wherein at least one CH ₂ group which is not contiguous is -O-, -S-, -NH-,- N (CH ₃ )-, -CO-, -O-CO-, -S-CO-, -O-COO-, -CO-S-, -CO-O-, -CH (halogen)-, -CH Or (CN)-, -CH = CH- or -C≡C-.

Typical spacer groups are, for example,-(CH ₂ ) _o -,-(CH ₂ CH ₂ O) _p -CH ₂ CH _2- , -CH ₂ CH ₂ -S-CH ₂ CH ₂ -or -CH ₂ CH ₂ —NH—CH ₂ CH ₂ —, where o is an integer from 2 to 12 and p is an integer from 1 to 3.

Preferred spacer groups are, for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene , Ethylene-thioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethylene, propenylene and butenylene.

Particular preference is given to compounds of the formula (1) of the invention in which Sp represents an alkylene or alkylene-oxy group having 2 to 8 carbon atoms. Straight chain groups are particularly preferred.

In another preferred embodiment of the invention, the chiral compound of formula 1 comprises at least one spacer group Sp which is a chiral group of the formula

Where

Q ¹ and Q ³ have the meaning given to Formula 3,

Q ⁴ is an alkylene or alkylene-oxy group having 1 to 10 carbon atoms or a single bond, and is different from Q ¹ .

When R represents P-Sp-X-, the two spacer groups Sp in the compound of Formula 1 may be the same or different.

Among the preferred compounds described above, compounds in which n is 1 are particularly preferred.

A compound containing both - are more preferred compounds in which n is 0, and the group P- (Sp-X) _n - and n is 1, and the group _n P- (Sp-X).

X is preferably -O- or a single bond.                     

Compounds of formula (I) of the present invention can be synthesized according to known methods or analogous to known methods, for example the methods of Houben-Wely (Methoden der organischen Chemie, Thieme-Verlag) , Stuttgart). Some specific manufacturing methods can be found in the examples.

The present invention also relates to polymerizable liquid crystal compositions comprising at least two polymerizable components, at least one of which is a compound of Formula 1, and to linear or crosslinked polymers prepared from the compounds and compositions of the present invention.

Suitable polymerizable mesogenic compounds that can be used as co-components of polymerizable liquid crystal compositions with the compounds of formula 1 of the present invention are described, for example, in WO 93/22397; European Patent No. 0 261 712; German Patent No. 195 04 224; International Publication No. WO 95/22586 and International Publication No. 97/00600. However, the compounds disclosed in these documents are merely regarded as examples and do not limit the scope of the present invention.

Typical examples of such polymerizable mesogenic compounds are shown in the following list of compounds, which are to be regarded only as examples and are not intended to limit the invention but to illustrate:

Where

P has one of the meanings of formula 1 and the above-mentioned preferred meanings,

x and y are each independently 1 to 12,

A is 1,4-phenylene or 1,4-cyclohexylene,

v is 0 or 1,

Z ⁰ is -COO-, -OCO-, -CH ₂ CH ₂ -or a single bond,

R ⁰ has one of the meanings of R in formula 1 and the above-mentioned preferred meanings,

L ¹ and L ² have one of the meanings provided above.

In a preferred embodiment of the invention, the polymerizable liquid crystal composition comprises at least one monoreactive compound of formula (I) and at least one double reactive or multiple reactive polymerizable compound, i.e. a mesogenic compound having at least two polymerizable groups. Include. Particular preference is given to double reactive compounds, ie compounds having two polymerizable groups. Very preferred are the dual reactive compounds of Formula 1 and Formulas 5a and 5b above.

In addition, the polymerizable liquid crystal composition of the present invention may include one or more non-polymerizable chiral compounds, which may be mesogenic or non-mesogenic, and may additionally or alternatively include chiral polymerizable compounds. For example, commercial dopants such as R 811 or R 1011 (available from Merck KGaA, Germany) can be used for this purpose.

Especially preferred are chiral dopants of the formulas (6) and (7) comprising each of the (R, R), (S, S), (S, R) and (R, S) enantiomers, unless otherwise indicated:

Where

E and F are each independently 1,4-phenylene or trans-1,4-cyclohexylene, which may be substituted by L ¹ as defined in Formula 1,

v is 0 or 1,

Z ⁰ is -COO-, -OCO-, -CH ₂ CH ₂ -or a single bond,

R ¹ is alkyl, alkoxy or alkanoyl having 1 to 12 carbon atoms.

Compounds of formula 6 and their synthesis are described in WO 98/00428. Compounds of formula (7) and their synthesis are described in British Patent No. 2,328,207. The chiral compounds of formulas (6) and (7) exhibit very high helical twisting power (HTP), and are therefore particularly useful for producing CLC polymer films with short helical pitches.

The polymerizable liquid crystal composition preferably contains 1 to 6, preferably 1 to 3, compounds of the formula (1).

In a preferred embodiment of the invention, the polymerizable liquid crystal composition comprises 1 to 80% by weight, preferably 2 to 60% by weight, in particular 5 to 50% by weight of at least one compound of the formula (1).

Particular preference is given to the following polymerizable liquid crystal compositions:

-a) 15 to 84.9% by weight, preferably 25 to 75% by weight, very preferably 35 to 65% by weight of at least one, preferably one, two or three compounds of formula 1,

b) 10 to 60% by weight, preferably 10 to 50% by weight, very preferably 15 to 1, at least one, preferably one or two double reactive polymerizable mesogenic compounds, preferably compounds of formula 5a or 5b 45% by weight,

c) 5 to 50% by weight, preferably 8 to 40% by weight of at least one, preferably one to four chiral and / or non-chiral, single reactive polymerizable mesogenic compounds, preferably compounds selected from formulas 5c to 5k %, Very preferably 12 to 35% by weight,

d) 0.1 to 5% by weight of initiator,

e) 0 to 10% by weight of one or more, preferably one or two chiral dopants, preferably 0.5 to 8% by weight, very preferably 0.2 to 4% by weight,

f) a polymerizable mixture comprising 0 to 5%, preferably 0.1 to 3%, very preferably 0.2 to 2% by weight of one or more dyes, preferably UV dyes;

-a) 15 to 75% by weight, preferably 25 to 70% by weight, very preferably 35 to 65% by weight of one or more, preferably one, two or three compounds of formula 1,

b) 0 to 40% by weight, preferably 0% by weight of one or more dual reactive polymerizable mesogenic compounds,

c) 15 to 85% by weight, preferably 20 to 70, of at least two, preferably two to six chiral and / or non-chiral single reactive polymerizable mesogenic compounds, preferably compounds selected from formulas 5c to 5k Weight percent, very preferably 25 to 65 weight percent,

d) 0.1 to 5% by weight of initiator,

e) 0 to 10% by weight of one or more, preferably one or two chiral dopants, preferably 0.5 to 8% by weight, very preferably 0.2 to 4% by weight,

f) a polymerizable mixture comprising 0 to 5% by weight, preferably 0.1 to 3% by weight, very preferably 0.2 to 2% by weight of one or more dyes, preferably UV dyes.

Liquid crystal polymers can be obtained from the polymerizable compounds and compositions of the present invention, for example by solution polymerization or in-situ polymerization.

For example, solution polymerization can be performed while heating at 30 to 60 ° C. for 24 hours using AIBN as an initiator in a solvent such as dichloromethane, tetrahydrofuran or toluene.

In-situ polymerization of the polymerizable liquid crystal compound and the composition is described by DJ Broer et al., Makromol. Chem. 190 , 2255 ff. and 3202ff. (1989).

The polymerizable liquid crystal compound and the composition according to the present invention are preferably polymerized in situ as described above and below.

The compounds of the present invention and polymerizable liquid crystal compositions are particularly useful for the production of anisotropic polymer films, such as nematic or cholesteric polymer films, having a constant molecular orientation.

Accordingly, another object of the present invention relates to an anisotropic polymer film having an oriented liquid crystal phase obtainable by polymerizing a polymerizable liquid crystal composition comprising at least one compound of the formula (1).

The polymerizable compounds and compositions of the present invention may be useful for the production of anisotropic polymer films having a tilted orientation, a splayed orientation, a planar orientation, a twisted orientation, or a homeotropic orientation.

For the sake of simplicity, optical films having oblique orientation, outwardly oriented, planar orientation, twisted orientation, or trend orientation are subsequently briefly referred to as 'inclined film', 'outwardly spreading film', 'planar film', 'twisted film' And 'trend film'.

The term 'inclined orientation' means that the optical axis of the film is inclined at an angle θ of 0 to 90 ° with respect to the film plane.

The term 'outwardly oriented orientation' means the inclined orientation defined above wherein the tilt angle further monotonously changes in the direction perpendicular to the film plane in the range of 0 to 90 °, preferably in the range of minimum to maximum.

The term 'planar orientation' means that the optical axis of the film is substantially parallel to the film plane. This definition also means that the optical axis is slightly inclined with an average tilt angle of 1 ° or less across the film relative to the film plane, and the optical axis is exactly the same as the film with a tilt angle of 0 °, which is exactly parallel to the film plane. And a film exhibiting properties.

The term 'twisted structure' relates to a film comprising one or more layers of liquid crystal material, wherein the mesogen is oriented along its main molecular axis in a preferred direction in the sublayer of the molecule and in such different sublayers The preferred orientation direction is twisted around the helix axis which is substantially perpendicular to the film plane, ie substantially parallel to the film vertical line. This definition also includes the orientation in which the helix axis is inclined at an angle of 2 ° or less with respect to the film vertical line.

The term 'oriented orientation' means that the optical axis of the film is substantially perpendicular to the film plane, ie substantially parallel to the film vertical line. This definition also includes a film whose optical axis is slightly inclined at an angle of 2 ° or less with respect to the film vertical line and a film that exhibits the same optical properties as the film whose optical axis is exactly equilibrated with respect to the film vertical line, i.

Twisted films, slanted films, outwardly spreading films and trending films can be used to reinforce and improve the optical properties of liquid crystal displays (LCDs), such as, for example, contrast ratios and gray scale displays at wide viewing angles. have. For example, in non-reinforced displays of the TN or STN type, frequent changes in gray density and gray scale conversion at wide viewing angles, as well as loss of contrast and undesirable changes in overall color are observed.

Optical retardants and reinforcing agents with twisted orientation and methods for their preparation are described, for example, in European Patent No. 0 423 881, European Patent No. 0 576 931 and US Patent No. 5,243,451. Optical reinforcing agents and retarders with twisted or outwardly oriented orientations are described, for example, in US Pat. No. 5,619,352, International Publication No. 97/44409, International Publication No. 97/44702, International Publication No. 97/44703 And International Publication No. 98/12584.

Twisted films with a high degree of twist exhibit selective reflection of circularly polarized light at the wavelength of visible light. The film can be used as a cholesteric or circular reflective polarizer, such as a notch polarizer or a broadband circular polarizer, or as a color filter. The film reflects a broad range of wavelengths of 200 nm or 300 nm or more, as described, for example, in European Patent 0 606 940, International Publication No. 97/35219 or European Patent No. 0 982 605, preferably It is especially useful as a broadband cholesteric polarizer covering the visible light spectrum. Thus, broadband cholesteric polarizers comprising the compounds of the present invention exhibit improved luminance gain. Color filters comprising the compounds of the present invention provide a broader reflection band.

The planar film is, for example, as a linear polarizer as described in EP 0 397 263 or as an optical retardant as described in WO 98/04651 (for example a quarter wavelength retardant). Can be used.

All disclosures of the aforementioned prior art documents are incorporated herein by reference.

In order to produce an anisotropic polymer film with a constant orientation, the polymerizable mesogenic compositions of the invention are preferably polymerized in situ by coating, aligning and exposing the substrate to heat or actinic radiation. Alignment and curing are preferably carried out in the liquid crystal phase of the composition.

Actinic radiation means irradiation with light such as UV, IR or visible light, irradiation with X-rays or gamma rays, or irradiation with high energy particles such as ions or electrons. As a source for actinic radiation, for example a single UV lamp or a set of UV lamps can be used. Possible sources for other actinic radiation are lasers such as UV lasers, IR lasers or visible light lasers.

In the case of polymerization by UV light, for example, a photoinitiator that decomposes under UV irradiation can be used to generate free radicals or ions that initiate the polymerization reaction. For example, when curing reactive mesogens having vinyl and epoxide reactive groups, it is also possible to use cationic photoinitiators which are photocured by cations instead of free radicals.

As photoinitiators for radical polymerization, commercially available Irgacure 651, Irgacure 184, Darocure 1173 or Darocure 4205 (all purchased from Ciba Geigy AG) While cationic photopolymerization can be used, commercially available UVI 6974 (purchased from Union Carbide) can be used.

The polymerizable liquid crystal composition preferably comprises a photoinitiator, particularly preferably 0.01 to 10% by weight, in particular 0.05 to 8% by weight, very preferably 0.1 to 5% by weight of the UV-photoinitiator.

In addition to the components mentioned above, the polymerizable composition may also comprise one or more other suitable components such as catalysts, stabilizers, chain transfer agents, co-react monomers or surface-active compounds. In particular, the addition of stabilizers is preferred, for example to prevent undesired spontaneous polymerization of the polymerizable material during storage.                     

As stabilizers, all compounds known to those skilled in the art for this purpose can be used in principle. Such compounds are commercially available in various varieties. Typical examples as stabilizers are 4-ethoxyphenol or butylated hydroxytoluene (BHT).

Other additives, such as chain transfer agents, may also be added to the polymerizable material to modify the physical properties of the polymer film of the present invention. When a chain transfer agent such as a monofunctional thiol compound (eg dodecane thiol) or a polyfunctional thiol compound (eg trimethylpropane tri (3-mercaptopropionate)) is added to the polymerizable material, The length of the free polymer chains and / or the length of the polymer chains between the two crosslinks in the polymer film of the invention can be controlled. When the amount of chain transfer agent is increased, the length of the polymer chain in the polymer film obtained is reduced.

In addition, in order to increase the crosslinking of the polymer, up to 20% of non-mesogenic compounds having two or more polymerizable functional groups are added to the polymerizable composition instead of or in addition to the di- or polyreactive mesogenic compounds. It is possible to do

Typical examples for bifunctional non-mesogenic monomers are alkyldiacrylates or alkyldimethacrylates having alkyl groups of 1 to 20 carbon atoms. Typical examples for non-mesogenic monomers having two or more polymerizable groups are trimethylpropanetrimethacrylate or pentaerythritol tetraacrylate.

The polymerizable liquid crystal composition may further include one or more other suitable components such as a catalyst, photosensitizer, stabilizer, surfactant, dye such as UV dye (which may also be polymerizable), chain transfer agent or co-reactive monomer.                     

In a preferred embodiment of the invention, the polymerization of the polymerizable composition is carried out under an atmosphere of inert gas, preferably under a nitrogen atmosphere.

As the substrate, for example, glass or quartz sheets as well as plastic films or sheets can be used. It is also possible to place a second substrate on top of the coated mixture prior to, during and / or after the polymerization. The substrate may or may not be removed after polymerization. If two substrates are used for curing by actinic radiation, at least one substrate should be transparent to the actinic radiation used for polymerization.

Isotropic or birefringent substrates may be used. In case the substrate is not removed from the polymerized film after polymerization, an isotropic substrate is preferably used.

Preferably, the at least one substrate is a plastic substrate, for example a film of polyester, such as polyethylene terephthalate (PET), a film of polyvinyl alcohol (PVA), a film of polycarbonate (PC), or triacetyl cellulose (TAC). ), Particularly preferably a PET film or a TAC film. As a birefringent substrate, for example, a uniaxially stretched plastic film can be used. For example, PET films are commercially available from ICI Corp. under the trade name Melinex.

In a preferred embodiment of the invention, the polymerizable composition of the invention is coated with a thin layer on the substrate or between two substrates and aligned in the liquid crystal phase to provide a constant orientation.

Constant orientation can be achieved, for example, by shearing the mixture (eg by a doctor blade). It is also possible to apply an alignment layer, for example a layer of rubbed polyimide or a layer of sputtered SiO _x , on one or more substrates. In some cases, the mixture spontaneously orients itself onto the substrate, or good alignment is already achieved by the action of covering the mixture. For example, planar alignment can also be achieved by adding a surfactant to the polymerizable composition, as described in WO 99/45082 A1.

In another preferred embodiment, the second substrate is placed on top of the coating material. In this case, the shear caused by putting the two substrates together is sufficient to provide good alignment. It is also possible to align the coating mixture by applying an electric or magnetic field.

In some cases, it is advantageous to apply a second substrate to exclude oxygen that may aid in the alignment of the polymerizable mixture or inhibit polymerization. Alternatively, curing may be carried out under an atmosphere of inert gas. However, curing in air is also possible using suitable photoinitiators and high lamp intensities. When cationic photoinitiators are used, oxygen exclusion is often not required but water should be excluded.

For example, in the preparation of an anisotropic polymer gel for use in a switchable liquid crystal display, the polymerizable compound or composition may be polymerized in situ as described above, but in this case the alignment of the polymerizable mixture is It may not be required even though it may be desirable for a particular use.                     

The invention also relates to polarizers, optical retardation or reinforcement films, alignment layers, color filters or holographic elements of the compounds, compositions and polymers of the invention; Liquid crystal displays such as PDLC, polymer gel or polymer stabilized cholesteric texture (PSTC) displays; Adhesives, synthetic resins having anisotropic mechanical properties, cosmetics, diagnostics or liquid crystal pigments; For decoration and protection; A non-linear optical or optical information storage. Compounds of the invention comprising chiral groups can also be used as chiral dopants.

The compounds of the invention of formula (1) are particularly suitable for the preparation of oriented liquid crystal polymer films which can be used as polarizing or reinforcing films in liquid crystal displays.

Without further effort, one of ordinary skill in the art would, using the foregoing description, utilize the present invention to its fullest extent. As a result, the following examples are merely examples and should not be taken as limiting the rest of the disclosure in any way.

In the preceding and subsequent examples, unless otherwise noted, all temperatures are given in uncorrected degrees Celsius, and all parts and percentages are by weight. The following abbreviations are used to describe the aspects of the liquid crystal phase of the compound: K = crystalline phase; N = nematic; S = smetic; Ch = cholesteric; I = isotropic. Numbers between symbols indicate phase transition temperature in degrees Celsius. Unless stated otherwise, the phase transition temperature is measured at a concentration of 5 to 10% by weight in the commercial nematic host mixture ZLI-4792 (manufactured by Merk Kgaa, Darmstadt, Germany).                     

EXAMPLE

Example 1

Compound (1) was prepared according to the following scheme:

compound R m Aspect on LC Δn ΔH (cal · mol ⁻¹ ) One C ₅ H ₁₁ 3 K 83 N 165 I 0.2577 2 C ₅ H ₁₁ 6 K 89 N 187 I 0.2800 K-I 7418 N-I233

1-1) 4-acetoxyphenyl iodide

4-iodophenol (25.0 g, 13.6 mmol) was dissolved in 3 M aqueous potassium hydroxide solution (56 mL, 170 mmol). Ice (150 g) was added followed by acetic anhydride (16 mL, 170 mmol). The mixture was shaken vigorously for 2 minutes, transferred to a separatory funnel and extracted with ethyl acetate (200 mL). The organic layer was removed, washed with water and dried (Na ₂ SO ₄ ). The solution was evaporated in a rotary evaporator to give a residual brown oil. Purification by flash chromatography yielded a colorless liquid (eluent DCM). Yield = 17.2 g, 72%. ¹ H-NMR and IR spectroscopy gave the expected signal.

1-2) 4- (4'-pentylphenyl) ethynyl phenol

4-isopentylphenylacetylene (10.5 g, 61.4 mmol), 4-acetoxyphenyl iodide (16.1 g, 61.4 mmol), catalytic amount of Pd (PPh ₃ ) ₂ Cl ₂ and catalytic amount of copper iodide at 70 ° C Stir in propylamine (100 mL). After 5 minutes, precipitation was observed and the mixture became incapable of stirring and toluene (100 mL) was added. The mixture was stirred at rt for 24 h and then evaporated on a rotary evaporator until dry. The residue was redissolved in aqueous potassium hydroxide ethanol solution and stirred at 70 ° C. overnight. The mixture was evaporated to dryness, then partitioned between ethyl acetate and water, the organic layer was removed, dried and evaporated. The residue was purified by flash column chromatography using DCM as eluent. Pink solid was obtained after evaporation of the appropriate fractions. Yield = 10.4 g, 64%. ¹ H-NMR and IR spectroscopy gave the expected signal.

1-3) 4- (oxyhexyl-3-chloropropanoyl) benzoyl chloride

3 drops of 4- (oxypropyl-3-chloropropanoyl) benzoic acid (5.0 g, 17.4 mmol), thionyl chloride (1.65 mL, 22.6 mmol, 1.3 equiv) and 3 drops of N-methyl pyrrolidone in DCM for 3 hours Stir under reflux. The solution was cooled and evaporated to dryness to give a colorless oil. Yield = 5.4 g, 100%. IR spectroscopy showed an appropriate signal. Samples were used in the next step without further purification.

1-4) 4-pentylphenyl ethynyl-4'-phenoxycarbonyl-4 "-phenoxypropyl acrylate (1a)

Acid chloride (5.3 g, 17.4 mmol) in step 1-3), phenol (4.6 g, 17.4 mmol) and triethylamine (14.6 mL, 104.4 mmol, 6 equivalents) in step 1-2) were added in DCM (150 mL). Stir at 35 ° C. overnight. The mixture was cooled to room temperature, washed with dilute aqueous hydrochloric acid solution and water, dried (Na ₂ SO ₄ ) and then evaporated to dryness on a rotary evaporator. The residue was purified by flash chromatography (eluent DCM: Petroleum ether 7: 3) to give a white shiny solid. Yield = 3.9 g, 86%. ¹ H-NMR and IR spectroscopy gave the expected signal.

Example 2

Additional compound (1) was prepared according to the following scheme 2:                     

compound R m Aspect on LC Δn 3 C ₃ H ₇ 3 K 86 N 188 I 0.26 4 C ₂ H ₅ 3 K 99 N 172 I 0.27 5 C ₇ H ₁₅ 3 K 88 N 176 I 0.25 6 C ₂ H ₅ 6 K 94 N 190 I 0.27 7 C ₃ H ₇ 6 K 83 N 180 I 0.25 8 C ₇ H ₁₅ 6 K 80 N 158 I 0.22 9 C ₄ H ₉ O 3 K 103 N 203 I 10 C ₄ H ₉ O 6 K 93 N 195 I 11 C ₆ H ₁₃ O 6 K 84 N 185 I 12 C ₂ H ₅ O 6 K 87 N 213 I 13 C ₆ H ₁₃ O 3 K 104 N 198 I

2-1) 4-iodophenyl 4- [3- (3-chloropropanoyl) oxy] propoxybenzoate

4- [3- (3-Chloro-propanoyloxy) -propoxy] -benzoic acid (26.2 g, 91.0 mmol), 4-iodophenol (20.0 g, 91.0 mmol) and TFAA (22.9 g, 109.2 mmol) Was dissolved in DCM (250 mL) and stirred under nitrogen for 3 h. The mixture was washed with dilute sodium hydrogen carbonate (2 x 200 mL) and water (200 mL), dried (Na ₂ SO ₄ ) and the solvent removed in vacuo to afford 4-iodophenyl 4- [3- (3-chloropro Panoyl) oxy] propoxybenzoate was obtained as a light brown solid (41.8 g, 85.5 mmol, 94%). ¹ H-NMR and IR spectroscopy gave the expected signal.

2-3) 4- [2- (4-propylphenyl) -1-ethynyl] phenyl 4- [3- (acryloyloxy) propoxy] benzoate

4-iodophenyl-4- [3- (3-chloropropanoyl) oxy] propoxybenzoate (12.22 g, 25 mmol) and triethylamine (31 mL, 222 mmol) were THF at room temperature for 24 hours under nitrogen atmosphere. It was stirred in (200 mL). The mixture was cooled to -4 ° C. Pd (PPh ₃ ) ₂ Cl ₂ (catalyst amount), copper iodide (catalyst amount) and 4-propylphenylacetylene (4.0 g, 27 mmol) were added. The mixture was allowed to warm to room temperature and then stirred for 48 hours. Water (500 mL) was added followed by ethyl acetate (500 mL). The organic layer was washed with saturated sodium chloride solution (500 mL), diluted hydrochloric acid (4 x 500 mL), water (500 mL) and saturated sodium chloride solution (500 mL) and dried (Na ₂ SO ₄ ). The solvent was removed in vacuo to give a yellow solid, which was purified by flash chromatography (3: 1 DCM / petroleum ether) and recrystallized from petroleum ether / ethyl acetate to give compound (3) as a white solid (7.47 g, 15.1 mmol). , 63.7%). Transition temperature: K-86-N-188-I; Δn = 0.26; IR (cm ⁻¹ ) 2956 (w), 2869 (w), 1741 (s);

According to the present invention, a polymerizable mesogenic compound having a wide liquid crystal phase and a high birefringence that can be used in the preparation of an oriented liquid crystal polymer film for optical applications can be broadened, thereby broadening the range of reactive mesogenic compounds available to the skilled person. .

Claims (20)

A polymerizable mesogenic tolan of formula (I) Formula 1

Where P is CH ₂ = CW-COO-,

Or CH ₂ ═CH-phenyl- (O) _k −, where W is H, CH ₃ or Cl, and k is 0 or 1, Sp is a spacer group having 1 to 25 carbon atoms, X is -O-, -S-, -CO-, -COO-, -OCO-, -CO-NH-, -NH-CO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O -, -SCH _2- , -CH ₂ S-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, -C≡C- or a single bond, n is 0 or 1, Z ¹ and Z ² are each independently -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -CH = CH-COO-,- OCO-CH = CH-, -C≡C- or a single bond, A ¹ and A ² are each independently 1,4-phenylene, wherein one or more CH groups may be substituted by N, 1,4-cyclohexylene, wherein one or two non-contiguous CH ₂ Groups may be substituted by O and / or S), 1,4-cyclohexenylene, 1,4-bicyclo (2,2,2) octylene, piperidine-1,4-diyl, naphthalene -2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydro-naphthalene-2,6-diyl, all such groups being unsubstituted, F, Cl, CN, Mono- or polysubstituted by OH, NO ₂ or an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, wherein one or more H atoms may be substituted by F or Cl, m1 and m2 are each independently 0, 1 or 2, the sum of m1 and m2 is 1 or 2, L ¹ and L ² are each independently F, Cl, CN, OH, NO ₂ or an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, wherein one or more H atoms may be substituted by F or Cl ego, r are each independently 0, 1, 2, 3 or 4, R is H, CN, halogen, or a straight or branched chain alkyl radical having 25 or less carbon atoms, which may be unsubstituted or mono- or polysubstituted by halogen or CN, wherein at least one non-contiguous CH ₂ group is Independently of each other in the case -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-,- CO-S- or -C≡C- may be substituted so that the oxygen atoms are not directly connected to each other), or alternatively R represents P- (Sp-X) _n- , only, a) P ₂ = CW-COO-, and the ^{CH, - (A 1 -Z 1)} m1 - and _{^{- (A 2 -Z 2) m2}} - phenylene either unsubstituted or substituted and the other is a single bond When R is P- (Sp-X) _n and / or n is 1, b) when the sum of m1 and m2 is 2, A ¹ and A ² are not cyclohexylene. The method of claim 1, _{^{- (A 1 -Z 1) m1}} - and _{^{- (Z 2 -A 2) m2}} - of one, or both, independently, to be connected via the radical Z groups tolran of formula I made by the general formula 2a to 2f and its mirror image to each other Polymeric mesogenic tolans selected from the group: Formula 2a

Formula 2b

Formula 2c

Formula 2d

Formula 2e

Formula 2f

Where Z is ^one of the meanings of Z ¹ in claim ¹ , L is independently at each occurrence a halogen, CN, OH, NO ₂ or an alkyl, alkoxy or alkanoyl group having 1 to 7 carbon atoms, wherein one or more H atoms may be substituted by F or Cl, r is 0, 1, 2, 3 or 4. The method of claim 1, A polymerizable mesogenic tolan characterized by m1 being 1 and m2 being 0. The method of claim 1, Polymeric mesogenic tolan, _wherein R represents P- (Sp-X) _n −. The method of claim 1, Polymeric mesogenic tolans wherein P is an acrylic group, methacryl group, vinyl group or epoxy group. The method of claim 1, Polymeric mesogenic tolan, wherein n is 1 and Sp is alkylene having 1 to 12 carbon atoms. A polymerizable liquid crystal composition comprising at least two polymerizable components, at least one of which is a compound according to claim 1. The method of claim 7, wherein At least one polymerizable mesogenic compound having at least two polymerizable end groups. The method of claim 8, a) 15 to 84.9 weight percent of one or more compounds of Formula 1, b) 10 to 60% by weight of at least one dual reactive polymerizable mesogenic compound, c) 5-50% by weight of one or more chiral and / or non-chiral monoreactive polymeric mesogenic compounds, d) 0.1 to 5% by weight of initiator, e) 0-10% by weight of one or more chiral dopants, f) 0-5% by weight of one or more dyes A composition comprising. A linear or crosslinked polymer obtained by polymerizing the compound according to claim 1. Linear or crosslinked polymer obtained by polymerizing the composition according to claim 7. delete An anisotropic polymer film comprising the polymerizable mesogenic tolan according to any one of claims 1 to 11, a polymerizable liquid crystal composition or a linear or crosslinked polymer. The method of claim 13, An anisotropic polymer film with twisted orientation, oblique orientation, outwardly oriented, planar orientation or homeotropic orientation. An optical reinforcing agent or retarder comprising the anisotropic polymer film according to claim 13. An optical viewing angle enhancer comprising the anisotropic polymer film according to claim 13 having an oblique orientation, an outward orientation or a trend orientation. A linear polarizer comprising the anisotropic polymer film according to claim 13. Circular reflective polarizer comprising the anisotropic polymer film according to claim 13. Color filter comprising the anisotropic polymer film according to claim 13. 20. A liquid crystal display comprising the reinforcing agent, retarder, polarizer or color filter according to any one of claims 14-19.