TW200305636A - Polymerisable compounds comprising a cinnamic acid group and an acetylene group - Google Patents

Abstract

The invention relates to new polymerisable mesogenic or liquid crystalline compounds comprising a cinnamic acid and an acetylene group, to polymerisable mesogenic or liquid crystalline mixtures and anisotropic polymers prepared thereof, and to the use of the new compounds and the mixtures and polymers prepared thereof in optical and electrooptical devices, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics, diagnostics, liquid crystal pigments, decorative and security applications, nonlinear optics, optical information storage, electronic devices like organic field effect transistors (FET or OFET), electroluminescent devices, or as chiral dopants.

Description

200305636 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a novel racemic polymerizable or liquid crystal compound containing cinnamic acid and an acetylene group, a racemic polymerizable or Liquid crystal mixture and anisotropic polymer prepared by the same, and this novel compound and mixture and polymer prepared by the other in optical and optoelectronic equipment, adhesives, synthetic resins with anisotropic mechanical properties, cosmetics, diagnostic methods , Liquid crystal pigments, decorative and safety applications, non-linear optics, optical data storage, electronic devices such as organic field-effect transistors (FET or OFET), electrical laser devices, or applications for palm-tree impurities. [Prior art] A racemic polymerizable or liquid crystal compound, which is also a conventional reactive racemic compound, has been described in the prior art for various applications. For example, they can be used to prepare linear or crosslinked liquid crystal side chain polymers. In addition, it can be aligned in its liquid crystal phase and then polymerized in situ to produce a high-quality uniformly aligned linear or crosslinked liquid crystal polymer film. This film can be used as a polarizer or compensator for optical elements such as flat panel displays, as described in, for example, EP 0 397 263, WO 98/00475, WO 98/0465 1 or WO 98/1 2584. Racemic polymerizable compounds have also been suggested for use in polymeric cholesteric liquid crystal films or coatings that selectively reflect visible light and are suitable as optical films such as narrow band or wide band reflective polarizers or color filters It is described, for example, in EP 0 606 940 or WO 97/35219, or the preparation of liquid crystal pigments is described in, for example, WO 97/30 13 6. An important area for other uses is the safety label (2) (2) 200305636, described for example in US 5,678,863 or anodized aluminum foil, described in, for example, GB 2,357,061. Other uses are as optical films for displays. Polymerizable compounds that produce racemic properties have been proposed for use in active, switchable layers of liquid crystal displays. For example, 'the conventional display can switch between transparent and scattering states' and consists of a low molecular weight liquid crystal (LC) medium and a phase-separated polymeric liquid crystal material, such as a PDLC (Polymeric Dispersive Liquid Crystal) display, described in WO 93 / 223 97, or a polymeric gel or polymeric mesh display of the scattering type, described in US 5,538,768, US 5,543,075 or EP 0 451905. In addition, the conventional low-molecular LC dielectric display can switch between two non-scattering states. The conventional display is, for example, TN or STN, ECB, VA or IPS mode, which can further include polymerized liquid crystal materials to create multiple structural regions. Structure, to improve the contrast or the difference in stable transition state in a wide viewing angle to reduce the driving voltage and switching time. The display is described in, for example, US 5,189,540, US 6,1 77,972, EP 0 903 392, and Hasebe et al., Jpn. J. Appl. Phys. 1994, 33, 6245. In the above applications, two A mixture of one or more racemic polymerizable compounds, because they have a lower melting point and a broader liquid crystal phase than a single compound. It is therefore necessary to exhibit a polymerizable mixture of a liquid crystal phase, preferably a nematic or a palmitic nematic phase at room temperature, so that they may be aligned and polymerized at a low temperature. For this purpose, it is very advantageous if a single polymerizable compound has exhibited a broad liquid crystal phase. When applied to the switchable layer of a liquid crystal display, it is usually mixed with a low molecular weight LC medium, so it produces the properties of a racemic polymerizable compound, -8-(3) (3) 200305636 such as the liquid crystal phase range and double refraction. It often needs to be similar to LC media. When used in a non-scattering switchable display, the polymeric material is not a macroscopic phase that can be separated from low molecular weight LC media, and the preferred polymerizable compound should show good miscibility with LC media. However, the racemic polymerizable compounds described in the prior art often often have a negative effect on the properties of the liquid crystal phase in LC mixtures, showing low solubility and adversely low birefringence in low molecular weight LC media. Prior art has reported that racemic polymerizable diphenylacetylene or phenylacetylene has a high double refraction 値 and has been disclosed in, for example, JP-A-0 5-3 3 9 1 8 9, JP-A-07-017910 , EP-A-0 659 865, JP-A-08-231958, JP-A_ 1 1 -147853, GB-A-2 35 1 734, JP-A-2000-281628, JP-A-2000-281629, and US-A-2002 / 0006479. However, the double refraction of such compounds is often not high enough, or often has a negative effect on the properties of the mixture when used in LC mixtures, or does not have sufficient stability against uV light. Therefore, 'the need for a racemic polymerizable compound without the above disadvantages', especially a compound having a high double refraction, can be used to prepare an oriented liquid crystal polymer film or to act as a switchable LC device in a mixture containing a low molecular weight LC medium. Layer of compounds. In addition, for the many uses of polymerizable compounds that produce racemic properties, experts need to obtain further compounds of this type that are both easy to synthesize and meet the needs described above. The object of the present invention is to provide a racemizable polymerizable compound having the above-mentioned advantageous properties, so as to provide experts with a racemic polymerizable compound -9-(4) (4) 200305636 species. Those skilled in the art can understand other objects of the present invention through the following detailed description. The polymerizable compound provided according to the present invention can achieve such an object. [Summary of the Invention] [Summary of the Invention] One of the objects of the present invention is a polymerizable compound of the formula I

p is a polymerizable group, SP is a spacer or a single bond, -0-, -S-, -CO-, -COO-, -OCO-, -QH-CH- f -0C0-0-, -S -CO-, -CO-S-, -CO-NR ^-, -NR ^ -CO-, -OCH2 ·, " CH2O ·, -SCH2-,-CH2S-, -CH ^ CH-COO-,- OOC-CH ^ CH-, CH2.CH2 or single bond, Z1 and Z2 are each independently-(: 00-, -0 (: 0-,-(: ^ 12 (: 112 ·, -〇CH2-,- CH20-, -SCH2-, -CH2S ·, -cf2o-, -ocf2 ·, -CF2S -... SCF2-, -CH2CH2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH = CH-, -CH = CH-, -CF = CH-, -CH = CF-, CF = CF-, -CH = CH-C00-, -0C0-CH = CH-, -CeC-, or single bond (5) (5) 200305636 A1 and A2 are each independently an aliphatic or aromatic carbocyclic or heterocyclic group (up to 16 C atoms, and may also contain fused rings), and may be unsubstituted, L-mono- or Multiple substitutions, ml and m2 are each independently 0, 1, 2 or 3, ml + m2 < 5, R is H, F, Cl, Br, I, CN, SCN, SF5, up to 25 C atoms Chain or branched alkyl, which may be unsubstituted, mono- or poly-substituted by F, Cl, Br, I, or CN, or it may be one or more non-adjacent The CH2 group is substituted, and in each case, it is independently: -〇-, -NH-, -NR0-, -SiR0R00-, -CO-, -COO ·, -OCO-, _ OCO-O-,- S-CO-'-CO-S-, -S〇2, -SO-O-, -O-SO-,. CH = CH_ or -CEC ·, in this method 0 and / or s atoms are not direct with each other Or P · S p-X, RQ and RGG are independently Η or 1 to 4 C atoms alkyl, L is F, Cl, Br, I, CN, NO2 or 1 to 7 C Atoms are alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy, in which one or more fluorene atoms may be substituted with F or C1, and 1 * is 0, 1, 2, 3, or 4. Another object of the present invention is a polymerizable liquid crystal mixture comprising at least one compound of formula I. Another object of the present invention is a polymerizable liquid crystal mixture prepared from one or more compounds of formula I or at least one compound of formula I, etc. Oriented polymer or polymer film. Another object of the present invention is to use polymerizable compounds of formula I, polymerizable mixtures, and polymers prepared therefrom for optical films, polarizers, -11-(6) ( 6) 200305636 Compensator, Beamsplitter, Inverter Film, alignment layer, color filter, holographic element, anodized aluminum foil, color image, decorative or security mark, liquid crystal pigment, adhesive, synthetic resin with anisotropic mechanical properties, cosmetics, diagnostic method , Non-linear optics, optical data storage, palm-tree hybrids, electronic devices such as field-effect transistor (FET) integrated circuit components, flat-panel thin-film transistors or radio frequency identification (RFID) tags, or organic light-emitting diodes (OLED) Semiconductor components, such as electric laser displays or backlight panels such as liquid crystal displays, photovoltaic or sensor devices, battery electrode materials, photoreceptors, or electrophotographic applications such as electrophotographic records. Another object of the invention is a liquid crystal display, the active layer of which comprises at least one compound of formula I or a mixture or polymer comprising at least one compound of formula I. [Definition of Terms] The term "film" herein includes self-sufficient (ie, free-standing) films, which show some significant mechanical stability and flexibility, and are on the support substrate or between the two substrates. Coating or layer. The term "racemic compound 1" as used herein shall mean a rod-, strip-, or disc-shaped racemic group, that is, a compound having a group capable of inducing a meso-phase. Such compounds do not necessarily have to exhibit mesophase properties by themselves. Such compounds may also exhibit mesophase properties only in mixtures with other compounds or when a racemic compound is produced or a mixture containing polymerization. Particularly preferred are racemic groups that are rod-shaped and strip-shaped. -12- (7) (7) 200305636 For the sake of simplicity, the term "liquid crystal material" in this article refers to the liquid crystal material and the material that produces racemization. The term "racemic agent" in this article refers to the material that produces racemic groups. . [Detailed Description of the Invention] The compound of the formula I is particularly suitable for use in polymerizable liquid crystal compositions. It can cause high double refraction. It has no meso phase property, but it can show meso when mixed with other compounds.相 性。 Phase properties. However, particularly preferred are compounds of formula I having a broad meso phase. In addition, the compounds of formula I show a tendency to inhibit the crystallization of the mixture and have improved UV stability. Particularly preferred compounds of formula I, wherein -ml + m2 = 1 or 2, -ml = m 2 = 0, -ml = m2 = 1, and A1 and A2 are aromatic groups, preferably ml or π2 is 1 -M is 1 and A1 is a phenylene group, in which one or more CH groups are substituted by N -Z1 and Z2 are selected from -COO-, -OCO- and -Ce C-, -r is 0, -r is 1 or 2, -r is 1 or 2, and L is F, -R is P-Sp-X --- Sp-X- is different from a single bond, -S p is 1 to 12 C atoms The alkylene group may be optionally substituted by F mono- or -13- (8) 200305636 and one or more non-adjacent CH2 may be substituted. In each case, they are independent of each other: -0-,- CH = CH- or -C = -C-, -X is -〇-, -COO-, -oco-, -OCOO-or a single bond, -Sp and X are single bonds, preferably L in formula I is F , Cl, CN, OH, N02, CH3 'C2H5, och3, oc2h5, coch3, coc2h5, cooch3, coc2H5, CF3, 0CF3, oCHF2 or oC2F5, especially f, Cl, CN, CH3, C2H5, QCH3, COCH3 or OCF3, the best being f, ci, CH, och3 or coch3. Preferred A1 and A2 in formula I are aromatic or cycloaliphatic% or 6_ rings, or a group containing two or three fused aromatic or cycloaliphatic 5 or 6_ rings, wherein such rings are also It may contain one or more heteroatoms, especially selected from N, O and S, and may also be mono- or multiple substituted by L. The preferred A1 and A2 in formula I are, for example, furan, pyrrole, thiophene, oxazole, thiawa, thiadiwa, miwa, phenylene, steep, pyrimidine, hydrazine, indan, naphthalene, tetrahydronaphthalene, Anthracene and phenanthrene. f 佳 夕 A 1 C1 and A2 ， 苴 保 湮 e

Monocyclic groups A1 and A2, and ml = m2. And the (A2-Z2) m2 group contains only the more preferable groups-(Α ^ Z1)-14-(9) (9) 200305636 πη- and-(Z2-A2) m2- are independently one or two Five- or six-membered ring groups. The groups-(A ^ Z1) ml • and-(Z2-A2) m2- can be the same or different. Particularly preferred compounds differ in-(A, Z)) and ((Z2 · A2) m2-. The preferred molecular formulas of the groups-(A ^ Z1) ml- and-(Z2-A2) M2 · are as follows. For simplicity, such groups have Phe as 1,4-phenylene, Phe l as 1,4-phenylene, which is substituted by 1 to 4 groups L as defined above, and Pyd is pyridine- 2,5-diyl and pyr are pyrimidine-2,5-diyl. The following preferred groups-(A ^ Z1) ml- and-(Z2-A2) m2- include the molecular formula ^ to π · 16 and its mirror image, which are linked to the diphenylacetylene of formula I via the group ζ Group. -Phe-Z- II-l -P yd-Z-II-2-P yr-Z-II-3 -PheL-Z- II-4 -Phe-Z-Phe-Z- II-5 -Phe-Z -Pyd-Z- II-6 -Pyd-Z-Phe-Z- II-7 -Phe-Z-Pyr-Z- II-8 -Pyr-Z-Phe-Z- II-9 -PheL-Z-Phe -Z- 11-10 -PheL-Z-Pyd-Z- 11-11 • PheL-Z-Pyr-Z- 11-12 > Pyr-Z-Pyd-Z- 11-13 -Pyd-Z-Pyd- Z- 11-14 (10) 200305636 -Pyr-Z-Pyr-Z- 11 -1 5 ^ PheL-Z-PheL-Z- 11-16 In such preferred groups, z is as z in formula I]. Preferably, z is -coo-, -OCO-, -CH2CH2, -CeC-or a single bond. In a more preferred group,-(A ^ Z1) ml-and-(Z2-A2) m2-are independently selected from the following molecular formulas and their mirror images, which are connected to the diphenylethynyl group of formula I via the group Z group.

lla lib lie lid lie I if

-16 · (11) 200305636 ^^-000- ^ 0 ^ 2- (L) r Μ iig llh where Z and L · have the same meanings as above, once r is 0, 1, 2, 3, or 4, the better is 〇, 1 or 2. The group-(A ^ Z1) ml- is linked to an acetylene group of the formula I,] ^ to 11 kn, preferably Z is a single bond, and ι \ (L) r L in such a preferred formula is preferably group w

L L L furthermore L wherein L is each independently n, or as defined above. Particularly preferred formulas are Ila, lie, Ilf, Iig, and llh, especially molecular formulas Ila, lid, and Ilf. Preferred compounds of formula I contain at least one group (L) r

Wherein r is a further preferred compound of formula I comprising at least two groups, wherein r is 1 and / or at least one group, and wherein r is 2. (L) r

R of Formula 1 is preferably an alkyl group, an alkoxy group, a thioalkyl group, a thiocarbonyl group, an alk-17- (12) 200305636 sulfonyl group or an alkenyl group. If R of Formula I is an alkyl or alkoxy group, i.e. terminal O-substituted, they may be straight or branched. Preferred is a straight chain having 2, 7, or 8 carbon atoms, according to which preferred are ethyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxypentyloxy, hexyloxy , Heptyloxy or octyloxy, other examples, decyl, carbonyl, dodecyl, tridecyl, pentadecyl, nonyl, decyl, undecyloxy , Tridecyloxy or tetradecyloxy. The oxaalkyl group, that is, the CH2 group is substituted by -0, preferably 2-oxopropyl (= methoxymethyl), 2-(= ethoxyheterobutyl (= 2-methoxyethyl) Radical), 2-, 3-, or 4-oxo 3-, 4-, or 5-oxhexyl, 2-, 3-, 4-, 5-, or 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 7- or 8-oxononyl or 2-, 3-, 4-, 5-, 6-, 7-, or. R is an alkylthio group, that is, the CH2 group attached to the alkyl group is substituted by -S-, and may be straight or branched. Compared with the straight chain of 3, 4, 5, 6, 7, or 8 carbon atoms And methylthio, ethylthio, propylthio, butylthiohexylthio, heptylthio, octylthio, further thio, decylthio, undecylalkyl Thio or dodecane If R is a thioindenyl or alkylthiocarbonyl group, that is, the CH2 group of the alkane group is replaced by -CO-S- or -S-CO, and the CH2 group is-, 3 , 4, 5, 6, propyl, butyl, butoxy, if it is methyl, nonyl, tetradecyloxy, twelve is straight chain, such as methyl) or 3-oxo, Heteropentyl, 2-,; 6-oxaheptyl, 4-, 5-, 6-, 8-, or 9-oxadecyl Bonding to adjacent groups is preferred. 1, 2 are preferred based on this, and amylthio is, for example, nonylthio. Basically linked to the phase It can be a straight chain or a branch of (13) (13) 200305636. Preferred are straight chains having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, and preferred based thereon are, for example, thioethylfluorenyl, thiopropylfluorenyl, thiobutanyl, thiopentyl Fluorenyl, thiohexyl, thioheptanyl, thiooctyl, methylthiocarbonyl, ethylthiocarbonyl, propylthiocarbonyl, butylthiocarbonyl, pentylthiocarbonyl, hexylthiocarbonyl Or heptylthiocarbonyl. If R is an alkanesulfonium group, that is, a CH2 group attached to an adjacent group on the alkyl group is substituted with a sulfonium group -SO2-, they may be straight-chain or branched. Preferred is a straight chain having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, and accordingly preferred are methyl fluorene, ethyl fluorene, propyl fluorene I, butyl fluorene, pentyl Base fluorene, hexyl fluorene, heptyl maple or octyl fluorene, others such as nonyl fluorene, decyl fluorene, undecyl fluorene or dodecyl fluorene. If R is an alkyl group in which one or more CH2 groups are substituted with -CH = CH-, they may be straight or branched. Preferred is a straight chain having 2 to 10 C atoms, and accordingly preferred is vinyl, prop-1-, or prop-2-enyl, but-1-, 2-, or but-3- Alkyl, pent-1-, 2-, 3 · or pent-4 · aryl, hex-1 ·, 2-, 3-, 4- or hex-5-enyl, hept-1 · 2-, 3, 4-, 5- or hept-6-alkenyl, octyl-1, 2-, 3-, 4-, 5-, 6- or oct-7-alkenyl, non-1, 2-, 3-, 4-, 5-, 6-, 7 · or non-8-alkenyl, dec-1., 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-alkenyl . Particularly preferred groups are C2-C7-1E-anal, C4-C7-3E ·· anal, C7_4-alkenyl, C6-C7-5-alkenyl, and C7-6-alkenyl, especially c2_c7_ iE-alkenyl, C4-C7-3E-alkenyl, and CvC7-4-alkenyl. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1L pentyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentyl Alkenyl, 3f -19- (14) (14) 200305636 hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4 Z-heptenyl, 5 -Hexenyl, 6-heptenyl and the like. In general, groups having up to 5 C atoms are preferred. If R is an alkyl group, one of the CH2 groups is replaced by -0 and one is replaced by a CO, such groups are preferably adjacent. Accordingly, such groups may together form an indenyloxy group -COO- or an oxycarbonyl group -0-CO. Preferred groups R are straight-chain and have 2 to 6 C atoms. Accordingly, preferred are ethenyloxy, propionyloxy, butyryloxy, pentamyloxy, hexyloxy, ethynyloxymethyl, propionyloxymethyl, and butyryl Oxymethyl, pentamyloxymethyl, 2-ethenyloxyethyl, 2-propenyloxyethyl, 2-butenyloxyethyl, 3-ethenyloxypropyl, 3-Propanyloxypropyl, 4-Acetyloxybutyl, Methoxycarbonyl, Ethyl and Ethyl, Propoxymine, Butoxy End Group, Amyloxy Phenyl, Methoxycarbonyl Methyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2 · (propoxy-carbonyl ) Ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl, 4- (methoxycarbonyl) -butyl. If R is an alkyl group in which two or more CH2 groups are substituted with -0- and / or -COO-, they may be linear or branched. Preferred is a straight chain having 3 to 12 c atoms. Accordingly, 'preferable ones are bis-carboxy · methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxypropyl, 4,4 · bis-carboxy · butyl, 5,5_ Bis-carboxy · pentyl, 6,6-bis-carboxy-hexyl, 7,7 · bis-carboxy-heptyl, 8,8 · bis-carboxy-octyl, 9,9-bis-carboxy · nonyl, 10,10-bis-carboxy-decyl, bis- (methoxycarbonyl) -methyl, 2,2 · bis- (methoxycarbonyl) -ethyl, 3,3-bis--20- (15) ( 15) 200305636 (methoxycarbonyl) -propyl, 4,4-bis- (methoxycarbonyl) -butyl, 5,5-bis- (methoxycarbonyl) -pentyl, 6,6-bis- (methyl (Oxycarbonyl) -hexyl, 7,7-bis. (Methoxycarbonyl) -heptyl, 8,8-bis- (methoxycarbonyl) -octyl, diethoxycarbonyl) -methyl, 2,2-bis (Ethoxycarbonyl) -ethyl, 3,3-bis- (ethoxycarbonyl) -propyl, 4,4-bis (ethoxycarbonyl) -butyl, 5,5-bis. (Ethoxycarbonyl)- Jiji. If R is an alkyl or alkenyl group, it is mono-substituted with CN or CF3, preferably a straight chain. CN or CF3 can be replaced at any desired position. If R is an alkyl or alkenyl group, it is at least mono-substituted with halogen, preferably linear. The preferred halogen is F or C1, and when multiple substitutions are preferred, f is preferred. The resulting groups also include perfluorinated groups. When F or C1 is monosubstituted, the substituent may be at any desired position, but preferably at the omega-position. Examples of particularly preferred terminal F-substituted linear groups are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-dihexyl and 7 -Fluoroheptyl. However, F in other positions is not excluded. A preferred halogen is F or C1. R of formula I may be a polar or non-polar group. When it is a polar group, it is a mono-oligo or polyfluorinated alkyl or alkoxy group selected from CN, SF5, halogen, OCH3, SCN, COR5, COOR5, or 1 to 4 C atoms. R5 is an alkyl group containing 1 to 4, preferably 1 to 3 C atoms, which can be fluorinated if necessary. Particularly preferred polar groups are selected from F, Cl, CN, OCH3, COCH3, coc2h5, cooch3, COOC2H5, cf3, chf2, ch2f, ocf3, 0CHF2, OCH2F, C2F5, and OC2F5, especially F, Cl, CN, CF3, OCHF2, and ocf3. When it is a non-polar group, it is preferably (16) (16) 200305636 an alkyl group having up to 15 C atoms or an alkoxy group having 2 to 15 C atoms. R of formula I may be a non-palatable or palmarized group. When it is a palm group, it is preferably selected from formula III: 夤

-Q -CH-Q Q3 in where Q1 is an alkylene or alkylene-oxy group or a single bond having 1 to 9 C atoms, Q2 is an alkyl or alkoxy group having 1 to 10 C atoms Groups, which may be unsubstituted, mono- or multiple substitutions by F, Cl, Br or CN, and may also be substituted by one or more non-adjacent CH2 groups, which in each case are independent of each other:- c = -c-, -0-, -S ·, -NH-, -N (CH3)-, -CO, -COO, -OCO, · 0 (: 00-, -S-CO or -COS-, In this way, the oxygen atoms are not directly connected to each other, Q3 is F, Cl, Br, CN, or an alkyl or alkoxy group, such as Q2, but different from Q2. When Q1 of Formula III is an alkylene-oxy group In this case, the 0 atom is preferably adjacent to the para-C atom. The preferred para-group in Formula III is 2-alkyl, 2-alkoxy, 2-methylalkyl, 2-methylalkoxy Radical, 2-fluoroalkyl, 2-fluoroalkoxy, 2- (2-acetylene) -sinyl, 2- (2-acetylene) -sinoxy, 1,1,1-trifluorosin and 1 (1,1-trifluoro-2-alkoxy). (17) (17) 200305636 A particularly preferable palm group is, for example, 2-butyl (= 1 -methylpropyl), 2-methyl Butyl, 2-methylpentyl, 3-methylpentyl, 2- Hexyl, 2-propylpentyl, especially 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy , 1-methylhexyloxy, 2 · octyloxy, 2-oxo-3-methylbutyl, 3-oxo-4-methylpentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxyoctyloxy, 6-methyloctyloxy, 6-methyloctyloxy, 5-formyl Heptyloxycarbonyl, 2-methylbutylfluorenyloxy, 3-methylpentamyloxy, 4-methylhexylfluorenyloxy, 2-chloropropanyloxy, 2-oxo-3-methyl Butylfluorenyloxy, 2-chloro-4-methylpentamyloxy, 2-chloro-3-methylpentamyloxy, 2-methyl-3-oxopentyl, 2-methyl- 3-oxahexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxy Propyl-2-oxy, fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2 · octyl And 2-fluoromethyloctyloxy. More preferred are 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2hexyl, 1,1 1_trifluoro-2-octyl and 1,1,1 · trifluoro-2-octyloxy. In addition, compounds of formula I which contain a non-parammitically branched group R, such as It may be important sometimes. Generally speaking, this type of branching group does not contain more than one side chain. The preferred non-palladium branching group is isopropyl, isobutyl (= methylpropyl ), Isoamyl (= 3-methylbutyl), isopropoxy, 2-methyl-propoxy, and 3-methylbutoxy. A preferred polymerizable or reactive group P is selected from: -23- (18) 200305636 ch2 = cw, coo, ο W2HC — CH — ο S ^ (CH2) k-0- CH2 = CW2. (0) kl-, ch3-ch = ch-〇-, (ch2 = ch) 2ch-oco, (ch2 = ch-ch2) 2CH-OCO, (ch2 = ch) 2CH-0-,

(ch2 = ch-ch2) 2n-, ho-cw2w3-, hs-cw2w3-, hw2n-, HO-CW2W3-NH-, CHfCW ^ CO-NH-, CH2 = CH- (coo) ki-Phe- (0 ) k2-, Phe-CH = CH-, HOOC-, OCN-, and W4W5W6Si, w1 is H, Cl, CN, phenyl, or an alkyl group of 1 to 5 C atoms, especially fluorene, Cl or CH3, W2 and W3 are independently alkyl groups of H or 1 to 5 C-atoms, especially methyl, ethyl or η-propyl. W4, W5 and W6 are independently Cl, 1 to 5 C- Atomic oxaalkyl or oxacarbonylalkyl, Phe is 1,4-phenylene, and h and k2 are independently 0 or 1.

Particularly preferred P is a vinyl group, an acrylate group, a methacrylate group, a propenyl ether group or an epoxy group, and particularly preferred is an acrylate or methacrylate group. As for the spacer group Sp, it can be all groups known to those skilled in the art. The preferred spacer group Sp is a linear or branched alkylene group having 1 to 20 C atoms, especially 尤其 to ^ C atoms. In addition, one or more non-adjacent CH2 groups may -〇-, -S-, -NH-, -N (CH3)-, -CO '-O-CO, -S-CO- -O-COO' -COS-, -COO-, -CH (halogen )-, -C (halogen) 2, -CH (CN)-, -CH = CH- or -CC-, or silyl group substitution. -24- (19) (19) 200305636 Representative spacer groups are, for example,-(CH2) p,-(CH2CH2O) r-CH2CH2-, -CH2CH2-S-CH2CH2- or -CH2CH2-NH-CH2CH2- or -(SiR ° R0 ° -〇) p-, P is an integer of 2 to 12, R is an integer of 1 to 3, and the meaning of R ° and RG () is as shown in Formula I. Preferred spacer groups are, for example, ethylene, propylene, butylene, pentenyl, hexyl, heptyl, octyl, oxonyl, decyl, and dodecyl. Carboalkyl, dodecane Alkylene, octadecylalkyl, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-methyl-iminoethylene, 1-methylalkylene, vinylene, vinylene Propylene and butylene. Other preferred compounds have one or two groups P-SP_X, where SP and / or X are single bonds. When the compound has two groups P-Sp-X, each two polymerizable groups P, two spacer groups S p, and two linking groups X may be the same or different. Formula I of the present invention is palm-like Another preferred embodiment of the compound comprises at least one spacer group Sp, which is a palmity group of formula IV: * -Q1_CH-Q4-

I

Q3 IV wherein Q1 and Q3 have the meanings as in formula 111 'and Q4 is an alkylene group or an alkylene-oxy group or a single bond of 1 to 10 C atoms, which is different from Q1. -25-(20) 200305636 Particularly preferred compounds of formula I are as follows

P-Sp-X

P-Sp-X

P-Sp-X

The meanings of P, Sp, X, R, L, and R are as above. · The above-mentioned compound is particularly preferable, wherein R is P-Sp-X, and wherein R is H or an alkyl group of 1 to 8 C-atoms. Compounds of formula I can be synthesized according to conventional or similar standard organic chemical methods, such as Houben-Weyl, Methoden de Rorganischen Chemie, Thieme-Verlag, Stuttgart. Some specific preparation methods can be found in the examples. The compounds of formula I can be used as liquid crystal mixtures in displays such as TN or STN displays, active matrix displays, VAN (vertical alignment nematic) in IPS (plane conversion) or VA (vertical alignment) mode or VAC (vertical alignment Calibrated cholesteric) display, ECB (electrically controlled birefringence), DAP (corrected phase deformation), CSH (color super segmentation) display or AS Μ (center-axis symmetrical cells) mode, phase change, guest-host , Flex-electric effect, flex-electric effect display, bistable nematic and cholesteric displays such as PSCT (polymer stabilized cholesteric texture), or PDLC, polymer gel or polymer mesh display . In particular, polymerizable compounds of formula I and mixtures containing them can be used in liquid crystal displays containing polymers or polymer network components to aid alignment, meso phase stability, and / or improve electro-optical properties, In particular, faster response times and / or lower threshold voltages can be achieved, or multi-structural region structures can be created to improve contrast over a wide viewing angle. The display is, for example, TN, STN, ECB, VA, IP S, multi-structure region or mixed mode, and is described in, for example, US 5,189,540, US 6,177,972, EP 0 903 392, and Hasebe et al., J ρ η · J. A pp 1 Phys · 1 9 9 4, 3 3, 6245. In addition, compounds of formula I are suitable as polymerizable ingredients in active broadband polymer-stabilized liquid crystal displays, as described, for example, in H. Guillard and P. Sixou. , Liq. Cryst. (2001) 28 (6), 933, the entire text of which is incorporated herein by reference. This type of display includes a -27- (22) (22) 200305636 active cholesteric layer with a broad reflective wavelength band that can switch between planar reflection, scattering, and segmented transparent states. Compounds of formula I are also suitable as polymer components for polymer-stable displays, such as bistable PSCT (polymer-stabilized cholesteric texture) displays, scattering-type or PDLC or polymer gel displays. Anisotropic polymer gels and displays containing them are disclosed, for example, in DE 195 04 224, GB 2 279 659, WO 93/22397, US 5,5 3 8,768, US 5,543,075 & SEP 0 45 1 905 ° Therefore, Another object of the invention is a liquid crystal mixture, especially a nematic liquid crystal mixture comprising at least one compound of formula I. Another object of the invention is a liquid crystal display comprising a liquid crystal medium, the liquid crystal medium comprising at least one compound of formula I. For use in the above applications, the liquid crystal mixture preferably contains at least one compound of formula I and a nematic host mixture, which contains one or more nematic or nematic compounds. Preferred liquid crystal mixtures are composed of 2 to 25, more preferably 3 to 15 compounds, at least one of which is a compound of formula I. Other compounds that form a nematic host mixture are preferably low molecular weight liquid crystal compounds, which are selected from nematic or can produce nematic substances, such as the conventional ones: oxyazobenzene, benzylidene-aniline, Biphenyl, bitriphenyl, phenyl or hexyl benzoate, phenyl or cyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexyl esters of cyclohexyl benzoic acid, cyclohexyl cyclohexyl residual acid Phenyl or cyclohexyl vinegar, benzoic acid, cyclohexanecarboxylic acid, and cyclohexylphenyl esters of cyclohexylcyclohexanecarboxylic acid, phenylcyclohexane, cyclohexyl-biphenyl, phenylcyclohexyl ring Hexane, cyclohex-28- (23) 200305636

Cyclohexane, cyclohexylcyclohexene, cyclohexylcyclohexylcyclohexene, 1,4-bis-cyclohexylbenzene, 4,4'-bis-cyclohexylbiphenyl, phenyl- or cyclohexylpyrimidine, benzene -Or cyclohexylpyridine, phenyl- or cyclohexylpyridazine, phenyl- or cyclohexyldihenane, phenyl- or cyclohexyl-1,3-dithioheptidine, 1,2-diphenyl- Ethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2- (4-phenylcyclohexyl) -ethane, 1-cyclohexylbiphenyl • Ethane, 1-phenyl 2-cyclohexyl • Phenylacetin 'can be halogenated blue, benzyl phenyl ether, diphenylacetylene, substituted cinnamic acid, and further nematic or nematic substance. The 1,4-phenylene group of such compounds may also be a mono- or difluoride in the transverse direction. A preferred embodiment of this liquid crystal mixture is a palmitic compound of this type. The most important compounds among the possible components of such liquid crystal mixtures are the following

R ·-L 丨 -G '-E-R, where L' and E can be the same or different, and they are independent of each other as follows:-Phe-, _Gyc-, Phe-Phe, Bu, Gyc Gyc_, pyr ·, -D1〇 ·, -B-Phe- and -B-Cyc · and bivalent groups formed by the mirror group thereof, wherein Phe is an unsubstituted or fluorine-substituted 14-phenylene group, Cyc Is trans-1,4-cyclohexenyl or 1,4-cyclohexenyl, pyr is pyrimidine-2, pyridyl or pyridin-2,5-monoyl, and 0 丨 〇 is 1,3-bis Kryptane_2,5_diyl,] 8 is 2- (trans-M-cyclohexyl) ethyl, pyrimidine · 2, diaryl, pyridine_2,5-diyl, or 1,3-dihumane- 2,5-diyl. -29- (24) 200305636 The G 'of this type of compound is selected from the following divalent groups: -CH = CH-, -N (O) Ν-, -CH = CY-, -CH = N (Ο)- , -C… = C-, CH2-CH2-, total O-, -CH2-〇-, -COS-,-CH 2 * S-,-CH = N-, -COOPhe-COO or single bond, Y system Is halogen, preferably chlorine or -CN. IT and R "are independent of each other: alkyl, alkenyl, alkoxy, alkenyloxy, alkylfluorenyloxy, alkoxycarbonyl or alkoxycarbonyloxy of 1 to 18 C atoms, preferably 3 to 12 C atoms, or another R 'and R "are F, CF3, 0CF3, Cl, NCS or CN. The R 'and R "of most of these compounds are each independently: alkyl, alkenyl or alkoxy groups with different chain lengths, where the sum of the C atoms of the nematic medium is generally between 2 and 9 Preferably, it is between 2 and 7. Many such compounds or mixtures are commercially available. All such compounds are known or can be prepared by known methods, and are suitable and suitable for this purpose. The exact reaction conditions for the reaction have been described in the literature (eg Η 〇ube η-Wey 1, Methoden deROrganischen Chemie [Methods of Organic

Chemistry], Georg-Thieme-Verlag, Stuttgart). Conventional variants can also be used, but will not be mentioned here. The compound of formula I and its polymerizable liquid crystal mixture can be further used for preparing anisotropic polymer films or coatings. When preparing an anisotropic polymer gel or polymer film, the liquid crystal mixture should contain at least one polymerizable compound, which may be a compound of formula I or an additional polymerizable or liquid crystal compound that produces racemization. Examples of suitable racemic polymerizable compounds that can be used as comonomers with compounds of formula IX in polymerizable liquid crystal mixtures are disclosed. -30- (25) (25) 200305636, for example, WO 93/223 97 EP 0,261,712; DE 1 95,04,224; WO 95/22586 and WO 97/00600. However, the compounds disclosed in such documents are merely examples and do not limit the scope of the invention. Preferred polymerizable liquid crystal mixtures include at least one racemic polymerizable compound having one polymerizable functional group and at least one racemic polymerizable compound having two or more polymerizable functions base. Particularly suitable examples of racemic and non-palatable polymerizable compounds are listed in the table below, however, they are only used to illustrate and not limit the present invention: -31-(26) 200305636

P- (CH2) xO ^ > ic00

Y (Va)

P «(CH2) xO COO

(Vb) p- (ch2) xo 乂] {coo k3 ^ r〇p- (ch2) x0 ^^ c〇〇-Kj ^ K5 ^ r, P- (CH2) x〇CH = CH-COO R ° ( Vc) (Vd) (Ve) CH2 = CHCOO (CH2) x 0 -o

(Vf) p- (ch2) xo

F) (F) (Vg) ~ Qr

p- (ch2) xo— (r > coo P ^ CHJO-V x > ~ COO

CH2CH (CH3) C2H5 CH2CH (CH3) C2Hs (Vh) (Vi) -32- 200305636 p (ch2):

〇 (CH2) P (Via), ~ Qr

P (CH2) xO >-ch2ch2 ^ ch2ch2 〇 (CH2) yP (Vlb) L2 (Vic)

P (CH2) xO

OOCCH = CH \ // 0 (CH2) yP

Or (Vld) (27) P- (CH2) x〇COO-Ter (Vk) P- (CH2) x〇 一 ^ COO-Chol (Vm) / ~ λ 丄 P- (CH2) x〇- ^ ( Vn)

(Vie) where the meaning of p is like formula i, the preferred meaning is as described above, x and y are the same or different integers 1 to 12, and A and D are 1,4-phenylene or 1,4-cyclohexyl- 33- (28) (28) 200305636 Alkenyl, v is 0 or 1, Y is a polar group, 1 ^ ° is a non-polar alkyl or alkoxy group, Ter is a terpene-like group such as s group, Choi L is a cholesterol group, and L1 and L2 are each independently an alkyl, alkoxy, alkylcarbonyl, or alkoxycarbonyl group of fluorene, F, Cl, OH, CN, NO2 or optionally 1 to 7 C atoms. The term "polar group f" herein is selected from the group consisting of F, Cl, CN, N02, OH, OCH3, OCN, SCN, up to 4 C atoms, optionally fluorinated carbonyl or carboxyl groups or 1 to 4 C Atomic mono-oligo or polyfluorinated alkyl or alkoxy groups. The term "polar group" herein means 1 or more, preferably 1 to 12 C atom alkyl groups or 2 or more, preferably 2 to 12 C atom alkoxy groups. The polymerizable liquid crystal mixture according to the present invention may contain one or more non-reactive palmarium impurities in addition to the racemic polymerizable compound. Typical palmar-branches are, for example, commercially available R or S 8 1 1, rulers or S 1011, R or S 2011 or CB 15 (Merck KGaA, Darmstadt, Germany). Even more preferred are palmarium hybrids with high helical rotation power (HTP), especially dopants containing sorbitol groups, which are described in WO 98/00428, and dopants containing hydrogen diphendione groups. The compounds are described in GB 2,328,207, the paranaphthyl binaphthyl derivatives are described in WO 02/94805, the paranaphthyl binaphthol acetals derivatives are described in WO 02/34739, and the palmar TADDOL derivatives are described in WO 02/06265, as well as palmitic compounds and terminal or central palmitic groups having at least one fluorinated linking group are described in WO 02/06 196 and WO 02/06195. In order to prepare anisotropic polymer films, polymerizable liquid crystals should be coated on -34- (29) (29) 200305636, in-situ calibration and polymerization, such as exposure to heat or actinic radiation ' To fix the orientation of liquid crystal molecules. Alignment and hardening are performed in the liquid crystal phase of the mixture. For example, the substrate can be a glass or quartz sheet or a plastic film or sheet, and it can be removed or not removed after polymerization. Suitable plastic substrates are, for example, polyethylene terephthalate (PET), polyvinyl alcohol (PVA), polycarbonate (PC), or triethyl cellulose (tac). Polymerizable palmitic LC materials can also be dissolved or dispersed in organic solvents before volatilization or during polymerization. For example, the alignment of the liquid crystal material can be achieved by treating the coating material's substrate, cutting the material during or after coating, applying a magnetic or electric field to the coated material, or adding a surface-active compound to the liquid crystal material. The δ-sequences of alignment techniques can be found in, for example, I. Sage in '' Thermotropic Liquid Crystals, edited by GW Gray, John Wiley & Sons, 1987, pages 75-77, and T. Uchida and H. Seki in " Liquid Crystals-Applications and Uses Vol. 3, ', edited by B.

Bahadur, World Scientific Publishing, Singapore 1 992, pages 1-63. A review of alignment materials and techniques can be found in, for example, J. Cognard, Mol. Cry st. Liq. Cryst. 78, Supplement 1 (1981), pages 1-77 ° Polymerization can occur when exposed to heat or actinic radiation . Actinic radiation refers to light irradiation, such as UV, IR or visible light, X-ray or gamma radiation, or high-energy particles, such as ion or electron irradiation. The preferred polymerization reaction is carried out at a non-absorbing wavelength under UV irradiation. Actinic radiation -35- (30) (30) 200305636 The source of the line is, for example, a single UV lamp or a group of UV lamps available. When using high power lamps, the hardening time can be reduced. Another possible source of actinic radiation is laser, such as UV laser, IR laser or visible laser. The polymerization is carried out in the presence of an initiator that absorbs the wavelength of the actinic radiation. For example, when the polymerization reaction is performed with UV light, the polymerization reaction can be initiated by a photoinitiator which is decomposed to generate groups or ions under UV irradiation. When curing polymerizable racemates containing acrylate or methacrylate groups, group photoinitiators should be used. When curing polymerizable racemates containing vinyl and epoxide groups, cationic properties should be used. Photoinitiator. It is also possible to use a polymerization initiator that generates groups or ions by thermal decomposition to initiate the polymerization reaction. The photopolymerization initiators that can be used are, for example, commercially available Irgacure 651, Irgacure 184, Darocure 1173 or Darocure 4205 (all from Ciba Geigy AG), and the cationic photoinitiator that can be used is commercially available UVI 6974 ( Union Carbide) The polymerizable material may additionally contain one or more other suitable ingredients, such as: catalysts, sensitizers, stabilizers, inhibitors, antioxidants, chain-transfer agents, co-reactive monomers, surface-active compounds , Lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, flow improvers, defoamers, oxygen scavengers, diluents, reactive diluents, adjuvants, colorants, dyes or pigments. Compounds of formula I containing a para palm group are suitable as para palmar hybrids. In addition, compounds of formula I with semiconductor or charge-carrying properties suitable as comonomers of liquid crystal materials can be applied to integrated circuit components of electronic devices such as field-effect transistors (FETs), thin-film transistors of flat-panel displays or without -36- (31) (31) 200305636 Wireline radio frequency identification (RFID) tag, or semiconductor component of organic light emitting diode (OLED) such as an electric laser display or a backlight such as a liquid crystal display, a photovoltaic or sensor device, a photoreceptor Or electronic photography recording device for electronic photography. For example, a semiconductor containing a polymerizable liquid crystal compound has been disclosed in WO 00/79617, JP-A-2000-347432, JP-A-11-209761,

Sirringhaus et al., Appl. Phy s. Lett., 77 (3) (2000) 406-408, and Grell et al., J. Korean Phys. Soc. 2000, 36 (6), 3 31. Liquid crystal materials used in electrical clock radios are described, for example, in WO 95/17018 and WO 95/04306. Liquid crystalline organic photoreceptors are described, for example, in EP 0 563 7 68 and EP 0 527 376. Without further explanation, those skilled in the art can use the present invention to make further improvements based on the above. Therefore, the following examples are only used to illustrate but not limit the scope of the present invention. In the foregoing and the following examples, unless otherwise specified, all temperatures are given by 'w'. All parts and percentages are expressed by weight. The following abbreviations are used to describe the properties of the liquid crystal phase of the compound: K = crystalline; N = nematic; s = fatty liquid crystal; Ch = cholesteric; 1 = isotropic. The number between the symbols means the phase transition temperature. C. In addition, mp · is the melting point, ^ is the optical anisotropy measured under 2000c, 5 89 um, and is the dielectric anisotropy measured at 20t, i kHz. [Embodiment] Example 1 -37- (32) 200305636 The preparation method of compound (1) is based on the following reaction scheme

Pd (PPh3) 2 / Mg / ZnBr2

⑴ The following compounds were prepared by a similar method -38- (33) 200305636 CH2 = CHC00 (CH2) 60

OMe (2) K92 Sa175N190I An = 0.3156

-39-

Claims (1)

200305636 ⑴ Patent application scope 1 · A polymerizable compound of formula I Where P is a polymerizable group, Sp is a spacer group or a single bond, 0 〆, X is-0-, -S-, -CO-, -COO_, -OCO-, -CH-CH-, _0C0_0_, _S_CO-, -CO-S-, -CO-NR. -, -NR'CO-, -OCH2-, _CH20 ·, _SCH2-, -CH2S_, -CH = CH-COO_, · OOCCH = CH-, (: 1 ^ €: 112 or single bond, Z1 and Z2 are each Independently -COO-, -OCO-, -CH2CH2-, -OCH2 ·, -CH2〇_, _SCH2 ·, -CH2S-, -CF2O-, -OCF2-,-CF2S-, -scf2-, -ch2ch2-, -CF2CH2-, -ch2cf2-,-CF2CF2_, _CH = CH_, -CH = CH ·, -CF = CH-, -CH = CF-, -CF = CF ·, -CH = CH-COO- ^ -OCO- CH = CH- '-C = -C- or single bond A1 and A2 are each independently an aliphatic or aromatic carbocyclic or heterocyclic group of up to 16 C atoms, which may also contain fused rings and May be unsubstituted, mono- or multiple-substituted by L, ml and m2 are each independently 0, 1, 2 or 3; ml + m2 < 5, R is H, F, Cl, Br, I, CN, SCN, SF5, up to 25 C-40- (2) (2) 200305636 atoms, straight or branched alkyl, which may be unsubstituted, mono-, F-, Cl-, Br, I or CN- or For multiple substitutions, one or more non-adjacent CH2 groups may also be taken by the following groups in such a way that 0 and / or S atoms are not directly connected to each other 'or to P-Sp-X In each case, they are independent of each other: -〇-, -S-, -NH-, -NR ...., -SiReR °, -CO-, -COO-, -OCO-, -OCO-O- , -SCO-, -CO-S-, -S02, -SO-O- '-O-SO-'-CH = CH-^-C =-C-j R ° and RRG are independent of each other as H or 1 Alkyl to 4 C atoms, L is F, C1, Br, I, CN, 1 ^ 02 or 1 to 7 C atom alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy Group, in which one or more fluorene atoms may be substituted by F or C1, and R is 0, 1, 2, 3, or 4. 2 · A polymerizable compound according to item 1 of the patent application range, wherein R is of formula I One of the definitions of P-Sp-X. 3. As for the polymerizable compound in the scope of patent application item 1 or 2, where ml + ni2 =: i or 2. 4 · As in the scope of patent application item 1 or 2 Polymerizable compound, wherein A 1 and A are selected from the group consisting of furan-2,5-diyl, thiophene-2,5-diyl, pyrrole-2,5-diyl, 1,4-phenylene, and pyridine- 2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-monoyl, n% [tetrahydro-naphthalene_2,6-diyl, hydroindane-2,5-diyl, And I, 4-cyclohexenyl, in addition, one or two non-adjacent The cH2 group may be substituted with 0 and / or s, and all such groups may be unsubstituted, mono- or multiple-substituted L as defined by Formula I. 5 · As for the polymerizable compound in the first or second scope of the patent application, its -41 · (3) 200305636-(A1-Z1) ml- and-(Z2-A2) m2- are independent of each other and are selected from The following molecular formula and its mirror image can be linked to the diphenylacetylene group of formula I via the group Z. Where L and r are as defined in Formula I, and Z is as Z1 in Formula I. -42-(4) 200305636 6. If the polymerizable compound of item 1 or 2 of the scope of patent application, it is selected from the following formula P-Sp-X 14 P-Sp-X 15 P-Sp-X 16 P-Sp-X COO 17 Among them, P, Sp, X, R, L and R have the same meanings as above. 7-A polymerizable liquid crystal mixture containing at least one compound as defined in the first patent application. 8. An anisotropic polymer or polymer film obtained from a polymerizable liquid crystal mixture as described in (7) (5) (5) 200305636 in the patent application. 9 · Use of at least one polymerizable liquid crystal material as claimed in claims 1 to 6, a mixture as claimed in claim 7 or a polymer or polymer film as claimed in claim 8, For optical films, polarizers, compensators, beam splitters, reflective films, alignment layers, color filters, holographic elements, anodized aluminum foil, color imaging, decorative or security markings, liquid crystal pigments , Adhesives, Synthetic resin with anisotropic mechanical properties, Cosmetics, Diagnostics, Nonlinear Optics, Opposite palm-tree hybrids for optical data storage, Components for integrated circuits of electronic devices such as field-effect transistor (FET), Flat panel Thin film transistors or radio frequency identification (RFID) tags on displays, or semiconductor components of organic light emitting diodes (OLEDs), such as electric laser displays or backlights, such as liquid crystal displays, battery electrode materials in photovoltaic or sensor devices Records used as photoreceptors or in electrophotography applications such as electrophotography. 10. A liquid crystal display having an active layer including at least one compound as claimed in the scope of the patent application, a mixture as the scope of the patent application, or a polymer or a polymer film as the scope of the patent application. -44- 200305636 Lu, (1), the designated representative of this case is: _ 圊 (II), the component representative symbols of this representative are simply explained: No, if there is a chemical formula in this case, please disclose the one that can best show the characteristics of the invention Chemical formula: The representative chemical formula designated in this case is: 丄 Chemical formula P-Sp-X-(A1-Z1) 5