DE19521457A1 - Polymeric acryloyloxyalkyl(oxy) biphenyl derivs. - Google Patents

Abstract

Polymeric cpds. of formula (I) are new. A = H or a gp. of formula CH2=CX1-COO-(CH2)m-(O)p- (gp. A1); B = H or a gp. of formula CH2=CX2-COO-(CH2)n-(O)q- (gp. B1); A and B cannot both = H at the same time; X1, X2 = H or Me; m,n = 0-14, p,q = 0 or 1; p = 0 if m = 0, and q = 0 if n = 0; Y1-Y4 = H or F. Also claimed are liq. crystal (LC) display elements with a pair of substrates (at least one of which is transparent) with a space between, and a LC layer in the space consisting of a LC zone surrounded by a wall of polymer; the LC layer contains a LC material, a polymeric material (II) and a polymeric cpd. (I).

Description

The present invention relates to polymeric compounds which in one Liquid crystal layer having a liquid crystal display element Polymer wall and a liquid crystal region which is essentially of is surrounded by the polymer wall, which limits the orientation Force of a liquid crystal material present in the liquid crystal areas than at an interface between the liquid crystal material and the polymer wall increased, and a liquid crystal using the polymeric compound stall display element. The liquid crystal display element according to the invention can display devices such as typewriter that are appealing to individuals machines, personal computers and the like are used. The liquid crystal display element can also be used in facilities designed by used by a variety of people such as portable information display devices and the like.  

Prior art liquid crystal display elements which have a flow Use sig crystal material and a polymer material

(1) Japanese Patent Application Laid-Open 58-501631 describes a Liquid crystal display element with dispersed polymer, which is a poly material and a liquid crystal material which is contained in the polymer material is encapsulated and the scattering state of the incident light over the difference in refractive index between the liquid crystal material and the polymer material and which indicates the transparent state by changing the refractive index of the liquid crystal material below that Indicates influence of an electrical voltage.

Japanese Patent Application Laid-Open 61-502128 describes a river sig crystal display element with a liquid crystal layer in which the phases three dimensions of the liquid crystal material and the hardened resin sional are separated that a mixture of the liquid crystal material and the light-curable resin has been irradiated with ultraviolet radiation.

These elements are basically liquid crystal display elements in which the Switching the light incident in the liquid crystal layer between Scattering and transparency is controlled electrically.

(2) Japanese Patent Application Laid-Open 1-269922 describes a Process for the production of liquid crystal regions with different Properties, which consists of a liquid crystal layer, which a photo-curable or photo-curable resin and a liquid crystal material includes irradiating with ultraviolet radiation through a photomask and After removing the photomask, the material again with ultraviolet rays irradiate lung. The element obtained in this way is essentially a litter-type element.

Japanese Patent Application Laid-Open 5-257135 describes one element with a liquid crystal layer obtained by substra te with an orientation film with an orientation limiting Force are equipped, forming a pair of columns opposite each other arranged horizontally, a mixture of a liquid crystal material and a  introduces photocurable resin into the column and then the mixture through a Ultraviolet photomask arranged on the surface of the substrate Radiation irradiated. Since the inner area of the liquid crystal layer in which the photomask is arranged compared to the outer area at Anle voltage and different threshold values shows different optical properties, the element is a static driver element in which the pixel pattern depending on the electrical voltage can be varied.

That of improving the viewing angle properties of a liquid principle underlying the crystal display element

To increase the appropriate viewing angle of a liquid crystal display element, it is necessary to orient each of the liquid crystal molecules within the pixels (liquid crystal regions) in three or more different directions. When each of the liquid crystal molecules is oriented or arranged in three or more different directions within the liquid crystal layer, the apparent refractive index of each of the liquid crystal molecules in the gray scale state is averaged when the pixels are in both the A and B directions as in of FIG. 1 (b) are shown, be seeks be. In other words, the contrast of the display element seen from both directions A and B is essentially identical. Therefore, the viewing angle characteristics of the element with such an orientation state of the liquid crystal as shown in FIG. 1 (b) are improved compared to the element with the TN mode shown in FIG. 2.

Specific examples of elements with a wide viewing angle

(1) Japanese Patent Application Laid-Open Nos. 4-338923 and 4-212928 describe display elements with a wide viewing angle in the form a combination of the above-mentioned liquid crystal element with dispersing polymer and polarizing plates on both surfaces of the Ele elements are arranged such that the polarization axes of the plates in rech angle.

(2) As a method for improving the viewing angle properties  non-scattering type liquid crystal element using a pola riser discloses Japanese Patent Application Laid-Open No. 5-27242 a method for producing a composite material from a river sig crystal and a polymer by phase separation of a mixture of the Liquid crystal and a photo-curable resin. Follow this procedure the orientation of the liquid crystal regions as a result of this made polymers statistically. As a result, there are the liquid crystal molecules at the time of applying an electric voltage in each area are oriented in different directions, by different rich observations of apparent refractive indices were essentially identical table, which verifies the viewing angle properties in the gray-scale state are better.

(3) In recent years, the present inventors have a liquid crystal Display element proposed with a liquid crystal area in which the Liquid crystal molecules in the areas where a photomask is present are oriented omnidirectionally (spiral), and one essentially from egg existing polymer wall in the other areas chen. The liquid crystal area and the polymer wall are thereby ge forms that a cell with a liquid crystal preparation, which the contains photo-curable resin and the liquid crystal material by photo irradiated mask. When the liquid crystal molecules of the liquid crystal display ge elements are controlled with an electrical voltage, the spi ral-shaped orientation of the liquid crystal molecules like opening and that Closing a screen, which signifi be improved.

At the interface between the polymer wall and the liquid crystal material of the element described in (3), the disclination lines are the reverse tilt of the liquid crystal molecules at the time of application generated against an electrical voltage. Since the declension lines as bright Lines are displayed, the viewing angle properties of the Ele ment deteriorates when the display state corresponds to the dark state speaks.

The present inventors have found that the addition of a polymeric ver  binding to a mixture of the liquid crystal material and the light-curing resin prevented the generation of the disclination lines in these elements different. However, by adding conventional polymeric compounds the pretilt angle of the liquid crystal material in the liquid crystal area Chen increases, which increases the brightness of the element in the absence of an elec trical voltage is reduced.

Therefore, the relationship between the Structure of the polymeric compound and the orientation of the liquid crystal molecules at the interface between the liquid crystal material and the Po lymerwandung examined, a compound was found with which one can form a liquid crystal display element which does not have discllinationsli nien generated bright display even in the absence of electrical voltage has properties.

The invention therefore relates to the polymeric compound according to claim 1 and the liquid crystal display element according to claim 8. The subclaims relate to particularly preferred embodiments of this counterpart of the invention befitting.

The polymeric compound of the invention generally corresponds to the following formula (I):

in which A is a hydrogen atom or a group of the formula

B represents a hydrogen atom or a group of the formula

X₁ and X₂ independently of one another are hydrogen atoms or methyl groups, m and n independently of one another are integers with values from 0 to 14,
p and q are independently 0 or 1 and
Y₁, Y₂, Y₃ and Y₄ independently of one another are hydrogen atoms or fluorine atoms with the proviso that A and B are not simultaneously hydrogen atoms, p is 0 if m is 0 and q is 0 if n is 0.

According to a preferred embodiment of the general formula (I):
A is a group of the formula:

and B is a group of the formula:

According to a further preferred embodiment, in general Formula (I) represents either A or B a hydrogen atom.

According to a further preferred embodiment, in the general formula (I)
A is a hydrogen atom or a group of the formula:

and B represents a hydrogen atom or a group of the formula:

According to a further preferred embodiment, both p and q the value 1.

According to a further preferred embodiment, in the general formula (I)
A is a group of the formula:

and B is a hydrogen atom.

Alternatively, A represents a hydrogen atom and B represents a group of the formula:

According to a further preferred embodiment of the connection of the general my formula (I) means at least one of the groups Y₁, Y₂, Y₃ and Y₄ Fluorine atom.

The liquid crystal display element according to the invention comprises a pair of Substrates arranged opposite to each other to form a gap are net, and a liquid crystal layer introduced into the gap. At least one of the substrates is transparent and the liquid crystal layer comprises one Liquid crystal region and a polymer surrounding the liquid crystal region wall, wherein the liquid crystal layer is a liquid crystal material, a poly meres polymer material and the polymeric compound described above closes.

According to a preferred embodiment of the invention, the liquid comprises crystal area liquid crystal molecules, the orientation of the liquid crystal stall molecules is either statistical, radial, concentric or spiral.

According to a preferred embodiment, the substrates are with a Orientation film covered.

According to a preferred embodiment, the liquid crystal region comprises Liquid crystal molecules, the orientation of the liquid crystal molecules in the TN, STN, ECB or FLC mode is available.

According to a preferred embodiment, the polymer Polymer material around a light-curable or photo-curable resin.  

According to a further preferred embodiment, the polymer corresponds A compound of general formula (I), wherein either A or B is water Matter atom means.

According to a further preferred embodiment, the polymer corresponds A compound of the general formula (I), in which A is a group of the formula:

and B is a group of the formula:

mean.

When a display mode is used using a limiting orientation Force on the substrate from a mixture of a liquid crystal material and a polymeric polymer material such as a photo-curable resin becomes gently, the orientation-limiting force of the orientation tends layer or alignment layer on the liquid crystal molecules as a result of Formation of a polymer layer consisting of the polymeric polymer material between between the orientation layer and the liquid crystal region, to be humiliated. However, if the polymeric Ver Binding is contained in the polymer layer, the ability of the transfer of the orientation-limiting force of the orientation layer on the Liquid crystal molecules inside the liquid crystal areas also in the buttocks Polymer layer enables the orientation of the liquid crystal molecules as a result of the presence of a material with a structure similar to that of the Liquid crystal material is stabilized in the polymer layer.

When the liquid crystal molecules present in the liquid crystal region are oriented symmetrically to the axis (an axis that is perpendicular to the surface of the substrate), when the voltage is applied, normally due to the reverse inclination (see Fig. 2), disclosure lines generated on the periphery of the liquid crystal region. However, the addition of the polymeric compound of the present invention causes the liquid crystal molecules to tilt forward on the substrate, so that the formation of disclination lines at the time of application of an electric voltage which affect the dark state is kept under control. As a result, a dramatic improvement in the contrast of the display element is achieved.

The present invention therefore enables the formation of a liquid crystal Display element with the following advantages.

• (1) Since the liquid crystal areas are surrounded by the polymer wall, the gap between the two substrates through the polymer wall keep right. As a result, it is possible to deform the liquid crystal Avoid display element under the influence of external forces and in particular avoid changing the color when a pen is on the surface of the element is pressed.
• (2) As a result of gravitational force, conventional liquid crystal displays show elements with large dimensions, which are arranged vertically, under different thicknesses in the lower and in the upper area. This leads to an un even display. Since the substrates of the liquid crystal according to the invention stall display element are fixed over the entire surface of the element, there is hardly any variation in the thickness of the cell.
• (3) It is possible to use the liquid crystal molecules in the liquid crystal range can be oriented statistically, concentrically, radially or spirally under effective use of phase separation between the liquid crystal material and essentially the best of the polymeric polymer materials polymer wall at the time of curing of the liquid crystal Composition. Because the liquid crystals of the liquid crystal areas are axis are oriented symmetrically, the liquid crystal obtained in this way shows Display element excellent viewing angle properties.
• (4) It is possible that the orientation limiting force at the interface between the liquid crystal material and the polymer layer using to enlarge the polymer compound of the invention.  
• (5) The liquid crystal display element of the invention is for display facilities aimed at a person, such as typewriters, personal nal computers and the like, suitable, as well as for display devices, which are aimed at a large number of people (especially those who a desk that is surrounded by 2 to 4 people), such as portable information display devices and the like.

The invention is detailed below with reference to the accompanying Drawings explained. The drawings show:

Fig. 1 is an enlarged view of the liquid crystal region of the erfindungsge MAESSEN liquid crystal display element;

Fig. 2 is a schematic diagram illustrating the observer angle properties of an element in TN mode;

Fig. 3 is a schematic diagram representing the disclination lines at the time of applying an electric voltage;

Fig. 4 is an enlarged view showing the liquid crystal region using a bifunctional polymeric compound;

Fig. An illustration of the photomask described in Example 9 5;

Fig. 6 is an enlarged view of the cell prepared according to Example 9;

FIG. 7 shows a series of graphs showing the electro-optical properties Ei (viewing angle characteristics) of the element prepared in Example 9 demonstrate; and

Fig. 8 shows a series of graphs that represent the electro-optical egg properties (viewing angle properties) of an element in TN mode.

The polymeric compound according to the invention has a functional group, which reacts with a polymeric polymer material, and closes monofunction  nelle polymeric compounds and polyfunctional polymeric compounds.

1. Monofunctional polymeric compounds A. Structure

The monofunctional polymeric compound is a compound that has a radio tional polymeric group in its molecule and attached to a mesogenic Group is bound with liquid crystal properties.

B. Effects

The following explanations clarify the effects that apply the polymeric compound can be achieved.

If a display device uses a to limit orientation force on the substrate from a mixture of a liquid crystal material and a polymeric polymer material, such as a photo-curable resin, the orientation-limiting force of the Orientie tends to be produced rungsfilm on the liquid crystal molecules in general by the formation ner polymer layer consisting of the polymeric polymer material between the Orientation layer and the liquid crystal region is formed, itself weaken. However, if the polymeric compound of the invention in The polymer layer is included, the ability to transfer the the orientation-limiting force of the orientation layer on the liquid crystal molecules within the liquid crystal area in the polymer layer maintained, thereby stabilizing the orientation of the liquid crystal molecules becomes. This is due to the presence of a material with a structure similar to that of the liquid crystal material in the polymer layer.

If the liquid crystal molecules present within the liquid crystal region are oriented symmetrically with respect to the axis (the axis X, which is shown in FIG. 1 (a) and which is at right angles to the surface of the substrate), will normally result the reverse slope at the time of applying an electric voltage, disclosure lines d (see Fig. 3) are generated on the periphery of the liquid crystal region. However, the addition of the polymeric compound of the present invention results in the liquid crystal molecules pretilting on the substrate so that the formation of the disclination lines at the time of application of an electrical voltage is kept under control (assuming that this is a consequence of the fact that that the liquid crystal molecules are oriented approximately at right angles at the time of application of an electrical voltage).

C. Influence of the change in chain length of the connecting groups in the polymeric compound

The number n and m of the connecting groups - (CH _2m - or - (CH₂) _n -, which connect the mesogenic group with the functional polymeric group, may affect the viewing angle properties of the liquid crystal display device produced in this way.

In the formulas given above, m and n have values from 0 to 14. Preference wise, m and n have values of 0 or 3 to 14, and more preferably 4 to 7. If both m and n are 2, the polymeric compound is too reactive for practice. If the values of m and n each exceed 14, he appear the mesogenic sections on the surfaces of the polymer wall and the polymer layer so that the response speed is reduced, assuming that it is a consequence of the fact that the mesogenic Groups are oriented in the same way as the liquid crystal molecules. Each the longer the chain length of the connecting groups, the smaller the Amount of polymeric compound required to achieve a limiting we The generation of the disclosure lines is necessary. At the same time however, the pre-tilt angle increases, which increases light transmission the cell is reduced. Therefore, it is necessary that the amount and the kind of polymeric compound can be selected in such a way that the disclosure lines kept under control and an increase in the angle of inclination be prevented.

D. Effect of fluorination of the polymeric compound on the view terwinkel properties of the element

In an element with a liquid crystal layer with a liquid crystal substrate  rich and a polymer wall surrounding the liquid crystal region, where at the liquid crystal area and the polymer wall through the phase centers Mixture of a liquid crystal material and a polymer Polymer material has been formed by the polymerization reaction the following problems (a) - (d) arise.

Problems and the causes assumed for them

• (a) Low response speed - dissolution of monomers of the Po polymer material in the liquid crystal;
• (b) Generation of the hysteresis effect - strong anchoring of the liquid crystal stall molecules on the polymer wall;
• (c) High driver voltage - same cause as given in (b);
• (d) Light scatter at the time a saturation voltage is applied - Dissolving the liquid crystal molecules in the polymer layer within the Liquid crystal area and strong anchoring of the liquid crystal molecules the polymer wall.

The causes of the problems mentioned above are a consequence of the strong ones Anchoring forces of the liquid crystal molecules on the polymer wall as well the good compatibility between the polymer material and the liquid crystal stall material. Both problems can be solved by using a fluorinated one polymeric compound can be overcome. Since it is assumed that the flu orated polymeric compound on the surfaces of the polymer wall and the Polymer layer appears, the orientation of the liquid crystal can stabilize be settled.

2. The polyfunctional polymeric compounds A. Structure

The polyfunctional polymeric compound is a compound in which one Large number of polymerizable functional groups on the mesogenic group are bound with liquid crystal properties. The number of functional  Groups is preferably 2. If it is 3 or more, the poly merwandung formed before the liquid crystal area in sufficient Has developed dimensions as a result of the fact that the gelling speed liquid crystal material is increased, with the result that the Light transmission of the liquid crystal display element in the absence of a electrical voltage is reduced.

The number n and m of the connecting groups - (CH₂) _m - or - (CH₂) _n - which bind the mesogenic group described above to the polymeric functional group are the same as for the monofunctional compound described above, but are preferably 12 or less. If the numbers exceed 12, the solubility of the polymeric compound in the liquid crystal material is reduced.

B. Effects

Like the monofunctional polymeric compound, the polyfunctional polymeric compound stabilizes the orientation of the liquid crystal molecules. In addition, the polyfunctional polymeric compound produces an observable image with respect to the generation of disclination lines, with an area showing a lesser degree of twisting, as shown in FIG. 4, than when using the mono functional polymeric compound achieved, and causes no disclosure lines at the time of application of an electrical voltage.

The use of a fluorinated polyfunctional polymeric compound gives the same effects as that of a monofunctional polymeric compound dung. In this case, the fluorinated area on the carbon inside of the mesogenic framework area.

3. Delay: d · Δn, where d is the thickness of the liquid crystal layer and Δn stand for birefringence

Since in the liquid crystal display element according to the invention with a Pola the liquid crystal molecules at the time of saturation voltage approximately perpendicular to the substrate (if Δε <0  is),

• (1) the polarizer has viewing angle properties and
• (2) the liquid crystal layer shows a delay of d · Δn.

This results in an area with poor viewing angle properties in the direction of 45 ° from the polarization axis of the polarizer.

The cause of the problem (2) mentioned above can be seen in the fact that the Light entering from the polarization direction of the polarizer, either only has a neat jet or just an extraordinary jet when passing through the refractive index ellipsoid of the liquid crystal layer, while the light coming in at 45 ° from the polarization axis of the polarizer falls, both a neat ray and an extraordinary ray which has the refractive index ellipsoid of the liquid crystal layer running. This causes the light to scatter or spread as a result of the el liptic polarization. It is therefore preferred that the delay by the Liquid crystal layer is as small as possible, so that there is no elliptical polar sation can result. Since the permeability T₀ in the absence of an electri voltage due to the delay through the liquid crystal layer is flowing, it is omnidirectional in terms of ensuring properties of the viewing angle properties and the brightness of the cell prefers that the delay of the liquid crystal layer be 300 nm to 650 nm wearing. If the retardation is less than 300 nm, the shows Cell in the absence of electrical voltage as a result of darkness Absence of brightness. It is therefore preferred that the angle of rotation Is 45 ° to 150 ° and in particular is close to 90 °, which makes it Most minimal conditions are met because the cell is at its greatest brightness shows its angle.

4. Liquid crystal display elements

The liquid crystal display element according to the invention comprises two substrates 1 a and 1 b, which are each arranged opposite one another with an intervening gap, and a liquid crystal layer 2 , which is present within the gap, as shown in FIG. 1. At least one of the two substrates 1 a and 1 b can be transparent. The liquid crystal layer 2 comprises a plurality of liquid crystal regions 20 and a polymer wall 21 surrounding the liquid crystal region 20 . For example, a liquid crystal display element is manufactured as follows.

Two substrates, which are provided with transparent electrodes, are arranged with a gap therebetween using a spacer to form a cell. Arranged on one side of the cell is a photo mask 3 , as shown in FIG. 5. Then, a liquid crystal composition containing a liquid crystal material, a polymeric polymer material and at least one of the above-described polymeric compounds is introduced into the cell. The cell is then irradiated with ultraviolet radiation through the side of the photomask, while an electrical voltage is applied to the transparent electrodes. As a result, the polymeric polymeric material and the polymeric compounds in the liquid crystal composition in the cell are polymerized and cured under the action of the ultraviolet radiation. In the polymerization process, the liquid crystal material and the polymeric polymer material in the liquid crystal composition are separated to form liquid crystal regions 20 which are surrounded by polymer walls consisting of the polymeric polymer material and polymeric compounds in the regions 30 which correspond to the photomask described above, as shown in FIG. 6.

The polymeric polymeric materials used for the display described above can be used include known polymerizable resins a, which are preferably light-curable or photo-curable resins.

These photo-curable resins include, for example, acrylic acids and acrylic latex with long chain alkyl groups with 3 or more carbon atoms or egg a benzene ring, including isobutyl acrylate, stearyl acrylate, lauryl acrylate, Isoamyl acrylate, n-butyl methacrylate, n-lauryl methacrylate, tridecyl methacrylic lat, 2-ethylhexyl acrylate, n-stearyl methacrylate, cyclohexyl methacrylate, Ben zyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl meth acrylate and the like. The light-curable resins also close polyfunctionally nelle resins that increase the physical strength of the polymer material hen, such as bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol methacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, neopentyldi  acrylate and the like.

5. Driver methods

The liquid crystal display element prepared in this way can be ver various driver methods are operated, such as single matrix and Active driver methods including, for example, a-Si, TFT, p-Si TFT, MIM and the like, but the driver method according to the invention is not be is particularly limited.

6. Substrate materials

The substrate materials to be used according to the invention include gla plates, plastic plates and the like, which are made of transparent solids fen and substrates with a thin metal layer, silicon Substrates and the like made from non-transparent solids are. The substrates with a thin metal layer are for liquid crystal pointing elements of the reflection type suitable.

The plastic substrate preferably consists of a material which visible light is not absorbed, including, for example, polyethylene tenter ephthalate (PET), acrylic polymers, polystyrenes, polycarbonates and the like. If a plastic substrate is used, the ability of the Polarisa tion are given to the substrate itself.

You can also use laminated substrates that you can combine of two types of different substrates or by laminating sub straten, which can be achieved by combining two substrates of either the same or different types with different thickness.

The following explanations schematically illustrate a method for manufacturing position of the polymeric compound described above. The following synthesis Sewege are only examples without the invention being restricted thereto should.  

7. Synthetic pathways Synthesis route 1

The compound of the general formula (I) is prepared:

according to the following scheme:

Synthesis route 2

The compound of general formula (I) is prepared, in which A and B represent the same group according to the following reaction scheme forth:

Synthesis route 3

The compound of general formula (I) is prepared in which either A or B represents a hydrogen atom, according to the following reak tion scheme:

Synthesis route 4

The intermediate compound is prepared according to fol reaction scheme

The synthesis routes 1 to 4 described above are explained in more detail below tert.

Synthesis route 1

The ver represented by the general formulas (1), (4), (5), (6), (7) and (8) bindings are commercially available. The connection of the general For mel (3), in which Y₁ and Y₂ each represent hydrogen atoms or fluorine atoms are commercially available.

The compound of general formula (1) with C₄H₉Li and then reacted with B (OCH₃) ₃ and hydrolyzed to form the compound of general formula (2), which is then oxidized with hydrogen peroxide to form bil extension of the compound of general formula (3).

The compound of general formula (3) with the compound of gen my formula (8) etherifies to form the compound of the general For mel (16), which is then esterified with the compound of the general formula (7), or the compound of general formula (3) is directly with the compound of the general formula (7) to form the compound of the general formula (17) esterified.

The compound of general formula (4) is with methoxymethyl chloride  (MOM-Cl) etherifies to form the compound of the general formula (13), then implemented with C₄H₉Li and then with B (OCH₃) ₃ and then hy is drolyzed to form the compound of general formula (15). The Compound of general formula (5) is further etherified with MOM-Cl to form the compound of general formula (14), which is then mixed with magne sium (Mg) is reacted to form a Grignard reagent. You can do that Compound of general formula (15) also obtained by that Reacts Grignard with B (OCH₃) ₃.

The compound of general formula (17), which can be with the help of the above procedure described, is in the presence of a palladium (Pd) catalyst coupled with the compound of general formula (15) to give the compound of general formula (18).

The methoxymethyl group (MOM) of the compound of the general formula (18) is split off under acidic conditions to form the compound of general formula (19), which then with the compound of general formula (8) or the compound of the general formula (12) (synthesis route 4) esterified or etherified to form the compound of general formula (I).

Synthesis route 2

The compound of general formula (20), which can be obtained by etherifying Ver Binding of the general formula (3) with MOM-Cl is obtained with the compound of the general formula (15), which can be determined using the above-described synthe sewegs 1, coupled in the presence of a Pd catalyst to form the compound of the general formula (21).

The MOM group of the compound of general formula (21) is under sau Ren split off conditions to form the compound of the general Formula (22). The compound of general formula (22) is with the verbin extension of the general formula (7) or the compound of the general formula (11) (Synthesis 4) esterified or etherified to form the compound of general formula (I), wherein A and B represent the same group.  

Synthesis route 3

The compound of general formula (1) is coupled with the compound of general formula (15) in the presence of a Pd catalyst to form the Compound of the general formula (23). The MOM group connecting the general formula (23) is split off under acidic conditions under Bil extension of the compound of general formula (24).

The compound of general formula (24) is then combined with the compound of general formula (8) or the compound of general formula (12) ver esters or etherifies to form the compound of the general formula (I), wherein either A or B represents a hydrogen atom.

Synthesis route 4

The commercially available compound of general formula (9) is with the Compound of general formula (7) esterified to form the compound of the general formula (11). The compound of general formula (10) is esterified with the compound of general formula (8) to form ver bond of the general formula (12).

Examples

The following examples serve to further explain the invention without however, restrict them.

The abbreviations used in the examples have the following meanings:

GC: gas chromatography
HPLC: high performance liquid chromatography
TLC: thin layer chromatography
IR: infrared absorption spectrum
F: melting point
GTO: glass tube furnace

example 1 Synthesis of the compound of the formula

A reactor is charged with 40 g of p-bromophenol and 200 ml of dimethylform amide (DMF) and 10 g of 60% sodium hydride (NaH) are gradually added. Then, while stirring at a temperature of 30 ° C or less, 18 g of methoxymethyl chloride is added to the solution and reacted overnight at room temperature to obtain a reaction solution. The reaction solution is poured into water, extracted with benzene, washed with water, dried over anhydrous sodium sulfate, the solvent is evaporated and the residue is distilled under reduced pressure. 38.4 g (yield = 79.3%) of 4-bromophenyl methoxy methyl ether are obtained.
Boiling point: 65-67 ° C / 0.6 mmHg
GC: 99.4%

(b) Synthesis of the compound of the formula

A reactor is charged under an argon flow with 100 g of 1,2-difluorine zol and 350 ml of tetrahydrofuran (THF) are then added dropwise with stirring a temperature of -50 ° C to -60 ° C 700 ml of a 1.6M C₄H₉Li- (butyllithium) - solution in hexane and stirred for 1 hour at the same temperature forming a solution. Then 175 g of trime are added dropwise thylborate (CH₃O) ₃B and stirred for 1 hour at room temperature.

The mixture is stirred overnight while maintaining the temperature and after lowered to room temperature. The mixture is then cooled to 0 ° C and adds dilute hydrochloric acid to the reaction solution.  

The reaction solution is extracted with toluene, washed with water, dried over anhydrous sodium sulfate, the solvent is evaporated, the crystalline residue is introduced into hexane and washed with hot hexane to give 80.8 g (yield = 56.6%) 2. 3-difluorophenylboric acid.
HPLC: 99.5%

(c) Synthesis of the compound of the formula

5.1 g of tetrakistriphe nylphosphine-palladium (Pd (PPh₃) ₄, 210 ml of a solution of 33 g of 4-bromophenyl methoxymethyl ether obtained in synthesis example (a) described above, in benzene, are charged to a reactor under an argon stream, 5.1 g 135 ml of an aqueous 2M Na₂CO₃ solution and 120 ml of an ethanolic solution of 24 g of 2,3-difluorophenylboric acid, which was obtained in synthesis step (b) described above, and stirred for 6 hours at reflux to form a reaction solution the reaction solution in water, extracted with toluene, washed with water, dried over anhydrous sodium sulfate, the solvent evaporated and the residue distilled under reduced pressure to give 20.1 g (yield = 53.6%) of 2,3-difluoro 4 ′ - (methoxymethyl) biphenyl.
Boiling point: 110-120 ° C / 0.25 mmHg
GC: 96.0%

(d) Synthesis of the compound of the formula

A reactor is charged with 20.1 g of 2,3-difluoro-4 '- (methoxymethyl) -biphenyl, which has been obtained in synthesis step (c) described above, 60 ml of THF and 90 ml of a 6N HCl solution and stirs at reflux for 3 hours. The reaction solution is cooled, extracted with toluene, washed with water, dried over anhydrous sodium sulfate, the solvent is evaporated off and the residue is distilled under reduced pressure, 9.0 g (yield = 54.3%) of 2.3- Difluoro-4'-hydroxybiphenyl receives.
Melting point: 160-170 ° C / 18 mmHg
F: 132-134.4 ° C
GC: 99.7%

(e) Synthesis of the compound of the formula

A reactor is charged with 4.0 g of 2,3-difluoro-4'-hydroxybiphenyl, which was obtained in synthesis step (d) described above, 2.0 g of triethylamine and 300 ml of benzene, and a solution of 1 is added dropwise , 9 g of acryloyl chloride in 100 ml of benzene and stirred for 5 hours. The reaction solution is washed with a 3N hydrochloric acid solution and then with water, then dried over anhydrous sodium sulfate, the solvent is evaporated and the residue is purified by column chromatography on silica gel (eluent: toluene) and then recrystallized from hexane to give 4.5 g ( Yield = 88.5%) 2,3-difluorobiphenyl-4'-yl-acrylate.
F: 88.4-90.0 ° C

The gas chromatographic purity of this material is 99.2%, that with HPLC measured purity 99.5%, while the thin layer chromato graphic only shows a stain. The infrared spectrum, the Mas spectrum that shows the molecular ion peak at 260, and the type of Starting materials make it clear that the compound mentioned is obtained has been.  

Example 2 (a) Synthesis of the compound of the formula CH₂ = CHCOO (CH₂) ₆Br

A reactor is charged with 30 g of 6-bromo-1-hexanol, 18.4 g of triethylamine and 500 ml of benzene, and a solution of 16.5 g of acryloyl chloride in 200 ml of benzene is added dropwise with stirring and cooling with ice. The mixture is stirred for 3 hours, washed with a 3N HCl solution and then with water, dried over anhydrous sodium sulfate, the solvent is evaporated, the residue is purified by column chromatography over silica gel (eluent: toluene) and 25.4 g (yield) = 65.1% 1 6-bromohexyl acrylate.
GC: 95.9%

(b) Synthesis of the compound of the formula

A reactor is charged with 4 g of the 2,3-difluoro-4'-hydroxybiphenyl obtained in the synthesis step (d) of Example 1 described above, 5.0 g of the 6-bromohexyl acrylate obtained in synthesis step (a) above, 5 , 4 g of K₂CO₃ and 400 ml of 2-butanone, refluxing for 28 hours, pouring the reaction solution into water, extracting with toluene, washing with water, drying over anhydrous sodium sulfate and evaporating the solvent. The residue is purified by column chromatography over silica gel (eluent: toluene) and crystallized twice from hexane to give 5.35 g (yield = 76.5%) 2,3-difluoro-4 '- [6- (acryloyloxy ) -hexyloxy] -biphenyl.
F: 45.6-46.8 ° C

The purity of this material is 99.0% as measured by gas chromatography and measured by HPLC 99.0%. The thin layer chromatogram shows just a stain. Based on the infrared spectrum, the fact that the mass spectrum shows the molecular ion peak at 360 and the type of out  gang materials can be seen that the above compound obtained has been.

Example 3 (a) Synthesis of the compound of the formula CH₂ = CHCOO (CH₂) ₁₂Br

The same procedure is used as in synthesis step (a) of the case game 1, with the difference that instead of 30 g of 6-bromo-1-hexanol 44.0 g of 12-bromo-1-dodecanol was used. 39.8 g are obtained (yield = 75.1%) 12-bromo dodecyl acrylate.

(b) Synthesis of the compound of the formula

The procedure of synthesis step (b) of Example 2 is repeated, with the difference that instead of 5.0 g of 6-bromohexyl acrylate, 6.7 g of 12-bromo-dodecyl acrylate are used, and 2.1 g (yield = 24.1%) ) 2,3-difluoro-4 '- [12- (acryloyloxy) dodecyloxy] biphenyl.
F: 59.7-60.7 ° C

The purity of the material measured by HPLC is 99.4%. The thin slice chromatogram shows only one spot. The IR spectrum, the The fact that the molecular ion peak observed at 444 in the mass spectrum and the type of raw materials used confirm the structure the above connection.  

Example 4 (a) Synthesis of the compound of the formula

A reactor is charged with 10.0 g of 4-bromophenol, 7.95 g of ethylene bromine in it, 16.0 g of K₂CO₃ and 300 ml of acetone, and the mixture is stirred at reflux for 50 hours. The reaction solution is poured into water, extracted with toluene, washed with water, dried over anhydrous sodium sulfate, the solvent is evaporated off, the residue is distilled under reduced pressure in a glass tube furnace (GTO) and 5.55 g (yield = 44.3 %) 1-bromo-4- (2-hydroxyethoxy) benzene.
GC: 96.8%
Boiling point: 100 ° C / 0.1 mmHg (corresponds to the prescribed temperature of the glass tube furnace).

(b) Synthesis of the compound of the formula

A reactor is charged with a solution of 5.0 g of 4- (2-hydroxyethyl) oxy-bromobenzene in 150 ml of benzene, 7.2 g of that obtained in step (b) of Example 1 Tenen 2,3-difluorophenyl boric acid, 68 ml of an aqueous 2M Na₂CO₃ solution and 1.0 g of Pd (PPh₃) ₄ and stirred at reflux for 9 hours. You pour it Reaction solution in water, extracted with toluene, washed with water, dried over anhydrous sodium sulfate, the solvent evaporates, the distilled Residue under reduced pressure in a glass tube furnace, crystallized from an ethanol / hexane mixture (1/1) to obtain 4.2 g (yield = 72.7 %) 2,3-difluoro-4 '- (2-hydroxyethoxy) biphenyl.  

(c) Synthesis of the compound of the formula

A reactor is charged with 2.0 g of the 2,3-difluoro-4 '- (2-hydroxyethoxy) biphenyl obtained in the above synthesis step (b), 0.9 g of triethylamine and 300 ml of diethyl ether, after which it is added dropwise under Stir and add 0.8 g of acryloyl chloride in 100 ml of diethyl ether while cooling with ice and stir for a further 4 hours. The reaction solution is washed with dilute hydrochloric acid and then with water, dried over anhydrous sodium sulfate, the solvent is evaporated, the residue is purified by column chromatography over silica gel (eluent: toluene) and 0.72 g (yield = 29.6%) 2.3 -Difluoro-4 '- [2- (acryloyloxy) ethoxy] biphenyl.
F: 47.4-50.1 ° C.

The purity of this material determined by HPLC is 99.4%. The thin slice chromatogram shows only one spot. Even the IR spectrum, the fact that the mass spectrum shows the molecular ion peak at 304, and the nature of the raw materials confirm receipt of the above compound dung.

Example 5 (a) Synthesis of the compound of the formula

A reactor is charged under a stream of argon with 2.1 g of Pd (PPh₃) ₄, one Solution of 11.6 g of 1-bromo-2,3-difluorobenzene in 100 ml of benzene, 60 ml of an aq Rigen 2M Na₂CO₃ solution and a solution of 13.3 g in the synthesis step (b) Example 1 obtained 2,3-difluorophenyl boric acid in 100 ml of ethanol and stir for 6 hours. The reaction solution is washed with a ver  dilute hydrochloric acid solution and then with water, dry over anhydrous sodium sulfate, the solvent evaporates and distills the Residue under reduced pressure to obtain 5.7 g (yield = 42%) 2,2 ', 3,3'-tetrafluorobiphenyl.

(b) Synthesis of the compound of the formula

One feeds a reactor under an argon stream with 5.7 g of that in the above gene synthesis stage (a) obtained 2,2 ', 3,3'-tetrafluorobiphenyl and 50 ml of tetra hydrofuran, gives dropwise at a temperature of -50 ° C or less 38 ml of a 1.6M solution of C₄H₉Li in hexane and stirred at this temperature during 2 hours, after which 10 g of trimethyl borate ((CH₃O) ₃B) are added dropwise added and gradually warmed to room temperature and stirred overnight.

Dilute sulfuric acid is added to the reactor, stirred for 1 hour and then extracted with ether, washed with water, dried over anhydrous sodium sulfate and the solvent evaporated. Hexane is added to the residue and washed with hexane to obtain a crystalline material, which is dissolved in 50 ml of tetrahydrofuran, after which 40 ml of a 10% aqueous H₂O₂ solution are added. The mixture is stirred overnight at room temperature, the reaction solution is extracted with toluene, washed with water, dehydrated with anhydrous sodium sulfate, the solvent is evaporated and 4.3 g of crude 2,2 ', 3,3'-tetrafluoro-4,4 are obtained '-Dihydroxybiphenyl.
GC: 92%

(c) Synthesis of the compound of the formula CH₂ = CHCOO (CH₂) ₈Br

The procedure of step (a) of Example 2 is repeated with the difference that 34.7 g of 8-bromo-1-octanol are used instead of 30 g of 6-bromo-1-hexanol, and 34.1 g ( Yield = 78%) 8-acryloyloxy-1-bromooctane.
GC: 97%

(d) Synthesis of the compound of the formula

A reactor is charged with 4.3 g of the synthesis described in the above stage (b) crude 2,2 ', 3,3'-tetrafluoro-4,4'-dihydroxybiphenyl obtained, 10.0 g 8-acryloyloxy-1-bromooctane, which is synthesized according to synthesis step (c) above received 7.8 g of K₂CO₃ and 30 ml of acetone and stirred for 16 hours on Reflux.

The reaction solution is filtered through a filter aid (high flow), toluene is added to the filtrate, washed with water, dried over anhydrous sodium sulfate, the solvent is evaporated, the residue is purified by column chromatography twice over silica gel (eluent: toluene / ethyl acetate = 20/1) and recrystallized from acetone, giving 1.28 g (yield = 12.9%) of 4,4′-bis [8- (acryloyloxy) octyloxy] -2,2 ′, 3,3′-tetrafluorobiphenyl.
F: 60.5-61.4 ° C

The purity of this material measured by HPLC is 99.7%. The thin slice chromatogram shows only one spot. The IR spectrum, the Fact that the mass spectrum shows the molecular ion peak at 622 and the type of materials used confirm receipt of the above connection dung.  

Example 6 Synthesis of the compound of the formula

The procedure described in synthesis stage (a) of Example 1 is repeated, with the difference that 30 g of 2,3-difluorophenol are used instead of 40 g of p-bromophenol. 32.6 g (yield = 81.4%) of methoxy methyl 2,3-difluorophenyl ether are obtained.
GC: 99.6%
Boiling point: 82-84 ° C / 14 mmHg

(b) Synthesis of the compound of the formula

The procedure of synthesis step (b) of Example 1 is repeated, with the difference that instead of 100 g of 1,2-difluorobenzene, 152.2 g of the methoxymethyl-2,3-difluorophenic nyl ether obtained in accordance with synthesis step (a) above is used . 150.6 (yield = 78.8%) of 2,3-difluoro-4- (methoxymethoxy) phenyl-boric acid are obtained.
HPLC: 97.4%

(c) Synthesis of the compound of the formula

The procedure of synthesis step (c) of Example 1 is repeated, with the difference that instead of 24 g of 2,3-difluorophenyl boric acid, 32.7 g of the 2,3-difluoro-4- obtained in synthesis step (b) above are (methoxymetho xy) phenyl boric acid used. 23.4 g (yield = 95.0%) of 2,3-di fluoro-4,4'-bis (methoxymethoxy) biphenyl are obtained.
GC: 96%

(d) Synthesis of the compound of the formula

The procedure of synthesis step (d) of Example 1 is repeated up to the step of distilling off the solvent, with the difference that instead of 20.1 g of 2,3-difluoro-4 '- (methoxymethoxy) biphenyl, 24.2 g of 2,3-difluoro-4,4'-bis (methoxy) obtained according to synthesis step (c) above methoxy) biphenyl used. 17 g of a residue (crude 2,3-di fluoro-4,4'-dihydroxybiphenyl).

(e) Synthesis of the compound of the formula

The procedure of synthesis step (d) of Example 1 is repeated, with the difference that instead of 4.3 g of 2,2 ', 3,3'-tetrafluoro-4,4'-dihydroxybiphenyl 3.6 g of the in the crude 2,3-difluoro-4,4'-dihydroxybiphenyl obtained in the synthesis step (d) described above is used. 1.0 g (yield = 10.5%) of 4,4′-bis [8- (acryloyloxy) octyloxy] -2,3-difluorobiphenyl are obtained.
Melting point: liquid at room temperature.

The purity of this material measured by HPLC is 99.0%. The thin slice chromatogram shows only one spot. Even the IR spectrum, the fact that the mass spectrum shows the molecular ion peak at 586 and the type of raw materials used confirm receipt of the obi connection.  

Example 7 (a) Synthesis of the compound of the formula

The procedure described in synthesis step (a) of Example 1 is repeated, with the difference that 43.9 g of 2-fluoro-4-bromophenol are used instead of 40 g of p-bromophenol. 46.7 g (yield = 86.4%) of methoxymethyl-4-bromo-2-fluorophenyl ether are obtained.
GC: 97.2%
Boiling point: 118-120 ° C / 14 mmHg

(b) Synthesis of the compound of the formula

A reactor is charged with 8 g of Mg and a few pieces of iodine, and a solution of 66 g of the methoxymethyl obtained in synthesis step (a) above is added. Drop 4-bromo-2-fluorophenyl ether in 300 ml THF (if necessary with heating), whereby a small amount is first added to the Re action. Then the rest of the solution is placed in tetra Hydrofuran dropwise with stirring and with boiling under reflux. To The dropwise addition is ended, the solution is stirred for a further 4 Hours at reflux to form a Grignard reagent.

Another reactor is charged with 54 g of (CH₃O₃) B and 200 ml of tetrahy drofuran, after which the Grignard reagent prepared in the manner described above is added dropwise with stirring at a temperature of 0 ° C. or less, after which it is gradually added It warms to room temperature and then stirred overnight. The reaction solution is poured into dilute sulfuric acid, extracted with ether, washed with cold water, dried over anhydrous sodium sulfate, the solvent is evaporated off and the residue is poured into hexane and washed with it to give 47.2 g (yield = 84.0%) ) 3-Fluoro-4- (methoxymethoxy) phenyl boric acid.
HPLC: 88.8%

(c) Synthesis of the compound of the formula

The procedure of synthesis step (c) of Example 1 is repeated, with the difference that instead of 24 g of 2,3-difluorophenylboric acid, 30 g of the 3-fluoro-4- (meth oxymethoxy) obtained in synthesis step (b) described above are used ) -phenyl-boric acid and, instead of 33 g of methoxymethyl-4-bromophenyl ether, 35.3 g of the methoxy-methyl-4-bromo-2-fluorophenyl ether obtained in synthesis step (a) above were used. 31.9 g (yield = 68.7%) of 3,3'-difluoro-4,4'-bis (methoxymethoxy) biphenyl are obtained.
GC: 99%
F: 76.3-77.3 ° C

(d) Synthesis of the compound of the formula

The procedure of synthesis stage (d) of Example 1 is repeated, with the difference that instead of 20.1 g of 2,3-difluoro-4 '- (methoxymethoxy) -biphenyl, 24 g of the one obtained in synthesis stage (c) above 3,3'-difluoro-4,4'-bis (methoxymethoxy) biphenyl used. 17.0 g (yield = 98%) of crude 3,3'-difluoro-4,4'-dihydroxybiphenyl are obtained.
GC: 99.6%

(e) Synthesis of the compound of the formula

The procedure of synthesis step (d) of Example 5 is repeated, with the difference that instead of 4.3 g of 2,2 ', 3,3'-tetrafluoro-4,4'-dihydroxybiphenyl 3.6 g of the in Synthesis stage (d) above obtained crude 3,3'-difluoro-4,4'-dihydroxybiphenyl used. 0.34 g (yield = 3.6%) of 3,3'-difluoro-4,4'-bis [8- (acryloyloxy) octyloxy] biphenyl are obtained.
F: 56.1-57.9 ° C

The purity of this material determined by HPLC is 99.5%. The thin slice chromatogram shows only one spot. The IR spectrum, the Fact that the mass spectrum shows the molecular ion peak at 586 and the type of starting materials used confirm receipt of the above Connection.

Example 8 (a) Synthesis of the compound of the formula

The procedure of synthesis step (c) of Example 1 is repeated, with the difference that instead of 24 g of 2,3-difluorophenyl boric acid, 32.7 g of the 2,3-difluoro- obtained after synthesis step (b) of Example 6 4- (meth oxymethoxy) phenyl boric acid and, instead of 33 g of methoxymethyl-4-bromophenyl ether, 35.7 g of the methoxymethyl-4-bromo-2-fluorophenyl ether obtained in synthesis stage (a) of Example 7 is used. 20.5 g (yield = 50%) of 2,3,3'-trifluoro-4,4'-bis (methoxymethoxy) biphenyl are obtained.
GC: 95%.

(b) Synthesis of the compound of the formula

The procedure of synthesis step (d) of Example 1 is repeated up to the distillation step with the difference that instead of 20.1 g of 2,3- Difluoro-4 '- (methoxymethoxy) biphenyl 21.7 g of the in the above synthesis step (a) 2,3,3'-trifluoro-4,4'-bis (methoxymethoxy) biphenyl used. 14.7 g of crude 2,3,3'-trifluoro-4,4'-dihydroxybiphenyl are obtained.

(e) Synthesis of the compound of the formula

The procedure of synthesis step (d) of Example 5 is repeated, with the difference that instead of 4.3 g of 2,2 ', 3,3'-tetrafluoro-4,4'-dihydroxybiphenyl 3.4 g of the in Synthesis step (b) above obtained crude 2,3,3'-trifluoro-4,4'-dihydroxybiphenyl used. 9 g (yield = 90%) of 2,3,3'-trifluoro-4,4'-bis [8- (acryloyloxy) octyloxy] biphenyl are obtained.
F: liquid at room temperature.

The purity of this material measured by HPLC is 99%. The thin slice chromatogram shows only one spot. The IR spectrum, the Fact that the mass spectrum shows the molecular ion peak at 604 and the type of starting materials used confirm receipt of the above Connection.

Examples 9 to 13 Liquid crystal display elements using a monofunctional polymeric liquid crystal material

A cell is formed using 1.1 mm thick glass substrates with transparent electrodes made of a mixture of indium oxide and tin oxide (ITO electrodes) with a thickness of 50 nm (500 Å) to form a gap with a width of 5 µm using a spacer. On one side of the cell prepared in this way, the photo mask 3 shown in FIG. 5 is applied. Furthermore, a uniform mixture of 0.65 g of stearyl acrylate, 0.15 g of 1,4-butanediol acrylate and 0.10 g of styrene, 0.10 g of the polymeric compound X, 13 given in Table 1 is injected using a capillary tube. 3 g of a liquid crystal material (ZLI-4792 from Merck, Inc .; Δn = 0.094) and 0.04 g of a photoinitiator (Irgacure 651).

Table 1

Applying an alternating voltage of 14 V to the transparent electrical the cell is irradiated for 8 minutes at 100 ° C. with parallel light from a high pressure mercury vapor lamp with an output of 10 mW / cm² (the ultraviolet radiation is allowed to act in such a way that there is a spatially regular pattern on the cell).

Then gradually cool the cell at a cooling rate of 10 ° C / h under applied electrical voltage to 25 ° C (at which temperature temperature of the liquid crystal is in the nematic state) and sets the loading radiation with the ultraviolet radiation continuously for 3 minutes to cure the resin and form a liquid crystal display element the.

If the display element obtained is observed under a polarizing microscope, it can be seen that the liquid crystal regions 20 have been formed in those regions which correspond to the photomask and that the liquid crystal molecules are arranged in a spiral around a central axis which runs in the center of the liquid crystal region, as shown in FIG. 6. A polarization plate is then attached to each substrate of the cell in such a way that the polarization planes are at right angles to one another. Fig. 7 shows the electro-optical properties in accordance with Example 11 receive NEN cell. The electro-optical properties of the cells obtained in the other examples (Examples 9, 10, 12 and 13) show the same trend as that shown in FIG. 7.

The formation of disclination lines is shown in the cells of Examples 9 to 11 kept perfectly under control while the cells of Examples 12 and 13 a few disclination lines are generated. Cell permeability Example 9 in the absence of applied voltage is significantly reduced, such as it is shown in Table 2. The higher the value of the number n the general Formula (I) is, the greater the permeability of the cell.

Table 2

Examples 14 to 17 Liquid crystal display elements using a bifunctional poly mer liquid crystal material

One brings in a in the same way as described in Examples 9 to 13 The cell produced a photomask in the manner described in Examples 9 to 13 written way. Then an egg is injected using a capillary tube ne uniform mixture of 0.75 g of stearyl acrylate, 0.10 g of styrene, 0.15 g of the in polymeric compound Y given in Table 3, 13.3 g of a liquid crystal  stall material (ZLI-4792 from Merck, Inc .; An = 0.094) and 0.04 g of one Photoinitiators (Irgacure 651) into the cell.

Table 3

The cell into which the mixture has been injected is then laid down with egg electrical voltage in the same manner as in Examples 9 to 13 be wrote, irradiated with ultraviolet radiation to a liquid crystal display ge element to form.

If one observes the element produced in this way with the aid of a polarization microscope, it can be seen that liquid crystal regions 20 have formed in the regions corresponding to the photomas ke that the liquid crystal molecules are arranged in a spiral around a central axis which is in the center of the liquid crystal region is located, and that areas with a lesser degree of twist have been generated in the vicinity of the liquid crystal regions, as shown in FIG. 4. If one arranges a polarizing plate on each substrate of the cell in such a way that the polarization planes are at right angles to one another, one can observe the same viewing angle properties as in the products of Examples 9 to 13.

If you continue to apply an electrical voltage to the formed element the formation of disclination lines cannot be observed. The Ta belle 4 illustrates the electro-optical properties of the in this way provided element.  

Table 4

As can be seen from Table 4, the cell of Example 17 shows that under An using a fluorinated bifunctional polymeric liquid crystal material has been produced, a lower light transmission when applying a voltage and shows excellent display characteristics. This is due to the fact that (1) the cell of Example 17 more double bre of the remaining liquid crystal materials shows as the cells of the case games 9 to 13 and that (2) the liquid crystal molecules when using the fluorinated liquid crystal material does not readily add to the substrates loosen the bound polymer film, which increases the anchoring strength at the Surface of the polymer film is reduced, as with the help of the polarization medium microscope can be observed.

Comparative Example 1

A photomask 3 shown in FIG. 5 is placed on the cell produced according to Example 9. In addition, a uniform mixture of 0.75 g of stearyl acrylate, 0.15 g of 1,4-butanediol acrylate, 0.10 g of styrene and 13.3 g of a liquid crystal material (ZLI-4792 from Merck, Inc .; Δn = 0.094) and 0.04 g of a photoinitiator (Irgacure 651) into the cell.

The cell is then irradiated using an electrical chip tion in the same way as described in Examples 9 to 13 with ultravio letter radiation to form a liquid crystal display element.  

If you look at the element made in this way, an electrical span application, so is the formation of the disclosure line under the polarization observing microscope. In addition, the light transmission is Cell when applying an electrical voltage 2.2%. Because this value is larger as that of the cells of Examples 14 to 17, it is believed that the Zu decrease in light transmission is a result of the generation of disclination lines is not.

Example 18

A polyimide film (AL4552, Nihon Synthetic Rubber, Inc.) is brought in with the help the spin coating process onto 1.1 mm thick glass substrates, the transparent electrodes made of a mixture of indium oxide and tin oxide (ITO electrodes with a thickness of 50 nm (500 Å)), and rubs this formed film with a nylon cloth. The two made in this way Substrates are attached to each other using a 5 µm spacer that the rubbing directions are at right angles to each other.

A photomask 3 shown in FIG. 5 is arranged on the surface of the cell prepared in this way. In addition, a uniform mixture of 0.55 g of stearyl acrylate, 0.15 g of 1,4-butanediol acrylate, 0.20 g of styrene and 0.10 g of the polymeric compound X, 13 used in Example 11 is injected using a capillary tube. 3 g of a liquid crystal material (ZLI-4792 from Merck, Inc.; Δn = 0.094; the twist angle of which was set to 90 ° using a chiral material S811) and 0.04 g of a photo initiator (Irgacure 651) into the cell . Then you prepare according to the method of Examples 9 to 13, a liquid crystal display element of the TN mode (Twisted Nematic Mode), the liquid crystal areas are surrounded by a polymer wall.

One fixes polarizing plates on both surfaces of the in this way manufactured element in such a way that the polarization axes of the Polarisa tion plates each correspond to the rubbing direction.

The liquid crystal of the element produced in this way lies in the TN Orientation in an even orientation state. In addition, especially  The display properties of the element do not riate, even when using a pin on the outer surface of the element.

Example 19

A polyimide film (Sunever; manufactured by Nissan Chemical, Inc.) is brought using a spin coating process on 1.1 mm thick glass substrate, the transparent electrodes made from a mixture of indium oxide and have tin oxide with a thickness of 50 nm (500 Å) (ITO electrodes), and subjects the material to rubbing with a nylon cloth. Man attaches the two substrates produced in this way via a 9 µm Ab stand against each other in such a way that the rubbing directions at an angle of 240 ° to each other.

A photomask 3 shown in FIG. 5 is arranged on the surface of the cell produced in this way. In addition, a uniform mixture of 0.55 g of stearyl acrylate, 0.15 g of 1,4-butanediol acrylate, 0.20 g of styrene and 0.10 g of the polymeric compound X, 13 used in Example 11 is injected using a capillary tube. 3 g of a liquid crystal material (ZLI-4427, manufactured by Merck, Inc .; whose drill angle was set to 240 ° using a chiral material, S811, and 0.04 g of a photoinitiator (Irgacure 651) in the cell. Subsequently, according to the method of Examples 9 to 13, a liquid crystal display element of the STN mode is prepared with liquid crystal regions which are surrounded by a polymer wall.

One fixes polarizing plates to both surfaces of the in this way manufactured element in such a way that the polarization axes of the Polarisa tion plates at an angle of, 45 ° to the rubbing direction and in one Angles of 105 ° to each other.

The liquid crystal of the element produced in this way lies in the STN Orientation before with uniform orientation state. In addition vari The display properties of the element do not change, even if you use a pin on the outer surface of the element.  

Example 20

A polyimide film (Sunever; manufactured by Nissan Chemical, Inc.) is brought using a spin coating process on 1.1 mm thick glass substrates with transparent electrodes made from a mixture of Indi umoxid and tin oxide with a thickness of 50 nm (500 Å) (ITO electrodes) verse hen and subjecting the layer to a rubbing treatment with a nylon cloth. The two substrates produced in this way are fastened under An using a 2 µm spacer so that the direction of friction are at right angles to each other.

A photomask 3 shown in FIG. 5 is attached to the surface of the cell produced in this way. In addition, a uniform mixture of 0.02 g of polyethylene glycol diacrylate (NK Ester A-200, manufactured by Shin-Nakamura Chemical Industries, Inc.), 0.09 g of lauryl acrylate, 0.01 g is injected using a capillary tube Styrene, 0.08 g of the polymeric compound X used in Example 11, 0.80 g of a liquid crystal material (ZLI-4003, manufactured by Merck, Inc.) and 0.005 g of a photoinitiator (Irgacure 651) into the cell. Then, according to the procedure described in Examples 9 to 13, a liquid crystal display element of the FLC mode (orientation of the SSF type) with liquid crystal areas surrounded by a polymer wall is prepared.

One fixes polarizing plates to both surfaces of the in this way prepared elements in such a way that the polarization axes of the Polarisa tion plates are at an angle of 90 ° to each other.

The liquid crystals of the element produced in this way are in the SSF orientation with a uniform orientation state. Furthermore The display properties do not vary, even if you put a pen on the outer surface of the element. Furthermore, there is no interference the orientation for common elements of the FLC mode when you click on a Surface of the element presses.

Claims (14)

1. Polymeric compound of the general formula (I): in which A is a hydrogen atom or a group of the formula B represents a hydrogen atom or a group of the formula X₁ and X₂ independently of one another are hydrogen atoms or methyl groups,
m and n independently of one another integers with values from 0 to 14,
p and q are independently 0 or 1 and
Y₁, Y₂, Y₃ and Y₄ independently of one another are hydrogen atoms or fluorine atoms with the proviso that A and B do not simultaneously mean hydrogen atoms, p is 0 when m is 0 and q is 0 when n is 0. 2. Polymeric compound according to claim 1 of the general formula (I), characterized in that A is a group of the formula and B is a group of the formula mean and
X₁ X₂, m, n, p and q have the meanings given in claim 1. 3. Polymeric compound according to claim 1 of the general formula (I), since characterized in that either A or B represent a hydrogen atom. 4. Polymeric compound according to claim 1 of the general formula (I), characterized in that A is a hydrogen atom or a group of the formula: and B represents a hydrogen atom or a group of the formula mean and X₁, X₂, m and n have the meanings given in claim 1 be. 5. Polymeric compound according to claim 2 of the general formula (I) since characterized in that both p and q have the value 1. 6. Polymeric compound according to claim 1 of the general formula (I), characterized in that A is a group of the formula: and B is a hydrogen atom or A is a hydrogen atom and B is a group of the formula mean and X₁, X₂, m and n have the meanings given in claim 1 be. 7. Polymeric compound according to claim 1 of the general formula (I), since  characterized in that at least one of the groups Y₁ Y₂, Y₃ and Y₄ Means fluorine atom. 8. Liquid crystal display element with a pair facing each other lying substrates spaced apart to form a gap are a liquid crystal layer in the gap, at least one of the Substrate is transparent and the liquid crystal layer is a liquid crystal area and a polymer wall surrounding the liquid crystal area has, characterized in that the liquid crystal layer is a liquid crystal stall material, a polymeric polymer material and a polymeric compound according to claim 1 contains. 9. Liquid crystal display element according to claim 8, characterized indicates that the liquid crystal region comprises liquid crystal molecules and the orientation of the liquid crystal molecules either statistical, radial, con is centric or spiral. 10. Liquid crystal display element according to claim 8, characterized indicates that an orientation film is placed on the substrate. 11. A liquid crystal display element according to claim 8, characterized indicates that the liquid crystal region comprises liquid crystal molecules and the orientation of the liquid crystal molecules a TN, STB, ECB or FLC Orientation is. 12. Liquid crystal display element according to claim 8, characterized indicates that the polymeric polymeric material is a photo-curable resin. 13. Liquid crystal display element according to claim 8, characterized records that the polymeric compound corresponds to the general formula (I), wherein A or B represent a hydrogen atom. 14. A liquid crystal display element according to claim 8, characterized in that the polymeric compound corresponds to the general formula (I) in which A is a group of the formula: and B is a group of the formula mean, wherein X₁, X₂, m, n, p and q have the meanings given in Claim 1 gene.