DE19521457C2 - Polymeric compounds based on acrylate and liquid crystal element containing them - Google Patents

Description

The present invention relates to polymeric compounds (depending on the context also to be understood as polymerizable compounds) that flow in one Liquid crystal display element with a poly merwandung and a liquid crystal region which is essentially of the Surrounded polymer wall, which is the force limiting the orientation of a liquid crystal material present in the liquid crystal regions an interface between the liquid crystal material and the polymer wall dung increased, as well as a liquid crystal using the polymeric compound Display element. The liquid crystal display element according to the invention can for Individual display devices such as typewriters and personal computers are used. The liquid crystal display element can also be used in facilities used by a variety of People are used as portable information display devices.

Prior art liquid crystal display elements using a liquid Use crystal material and a polymer material

(1) JP 58-501631 disclosed describes a liquid crystal display dispersed polymer element comprising a polymer material and a liquid comprises crystal material which is encapsulated in the polymer material and the Scattered state of the incident light over the difference in refraction index between the liquid crystal material and the polymer material and the transparent state by changing the refractive index of the Liquid crystal material under the influence of an electrical voltage displays.

JP 61-502128 discloses a liquid crystal display element with a liquid crystal layer in which the phases from the liquid crystal material and the hardened resin are three-dimensionally separated in that a mixture of the liquid crystal material and the photo-curable resin has been irradiated with ultraviolet radiation.

These elements are liquid crystal display elements in which the switching direction of the light falling into the liquid crystal layer between scattering and transparency is controlled electrically.  

(2) JP 1-269922, which is disclosed, describes a manufacturing process of liquid crystal areas with different properties, that in it there is first a liquid crystal layer, which is a light-curable or photocurable resin and a liquid crystal material by photo to be irradiated with ultraviolet radiation and after removal of the mask Photomask to irradiate the material again with ultraviolet radiation. The element obtained in this way is essentially an element of Litter type.

Laid-open JP 5-257135 describes an element with a liquid crystal layer obtained by making substrates with an orien film are equipped with a force limiting orientation, arranges opposite each other to form a pair of columns, one Mixture of a liquid crystal material and a photo curable resin in introduces the gap and then the mixture through a on the surface of the Substrate arranged photomask irradiated with ultraviolet radiation. There the inner area of the liquid crystal layer in which the photomask is arranged is net, compared to the outer area when applying an electrical Voltage different thresholds and different optical Shows properties, the element is a static one Driver element in which the pixel pattern depending on the electrical Voltage can be varied.

DE 42 26 994 A1 describes anisotropic polymers which are obtained by in-situ crosslinking of mesogenic monomers of the GAMAG structure in the liquid-crystalline phase state. The symbols G, A and M can have the following meanings:

G = acrylic or methacrylic
A = - (CH ₂ ) _m -; - (CH ₂ ) _m -O- or - (CH ₂ -CH ₂ -O) _n - (m = 1-16; n = 1-10)
M = biphenyl with substituents (R) _y (R = halogen; y = 1-4)

In the publication "D. Demus, H. Demus and H. Zaschke: Liquid Crystals in tables; Chapter 4; German Verlag f. Basic industry, Leipzig 1975 ", are di Verse biphenyl derivatives disclosed, but not those with (meth) acrylic ester groups.  

In GB 22 67 501 liquid crystal polymers based on forked Acrylate side chains described.

In the publication "H. Kelker, R. Hatz: Handbook of Liquid Crystals; chapter 2; Verlag Chemie, Weinheim 1980" liquid crystal materials with the basic structure XC ₆ H ₄ -ABC ₆ H ₄ -Y (X, Y end groups, AB = Bridge group) described.

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 shown in are considered in Fig. 1 (b) are shown. 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 a state of orientation 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) JP 4-338 923 and JP 4-212 928 which are disclosed describe display elements with a wide viewing angle in the form of a combination of the above mentioned liquid crystal elements with dispersed polymer and polarize the plates arranged on both surfaces of the element in such a way that the polarization axes of the plates are at right angles to each other.

(2) As a method to improve the viewing angle properties of a non-scattering type liquid crystal element using one Polarizing device, JP 5-27 242, discloses a method for  Production of a composite material from a liquid crystal and a poly mer by phase separation of a mixture of the liquid crystal and a photo-curable resin. The orientation of the Liquid crystal areas as a result of the polymer thus produced statistically. Accordingly, since the liquid crystal molecules at the time of Applying an electrical voltage in each area in different Directions are oriented that observe from different directions Apparent refractive indices are essentially identical, which makes the Viewer angle properties in the gray scale state are improved.

(3) A liquid crystal display element has been proposed in recent years beat with a liquid crystal area in which the liquid crystal molecules in the areas where a photomask is present, omnidirectional (spiral shaped) are oriented, and one essentially from a light-curable Resin existing polymer wall in the other areas. The liquid The crystal region and the polymer wall are formed by a cell with a liquid crystal preparation containing the photo-curable resin and containing the liquid crystal material, irradiated through a photomask. If the liquid crystal molecules of the liquid crystal display element with an elec trical voltage, the spiral orientation works of liquid crystal molecules like opening and closing a screen, which significantly improves the viewing angle properties.

At the interface between the polymer wall and the liquid crystal The disclination lines become the material of the element described in (3) due to the reverse inclination of the liquid crystal molecules at the time of Application of an electrical voltage generated. Since the disclosure lines as bright lines appear, the viewer's angle properties Elements deteriorate when the display state is dark speaks.

It has been found that the addition of a polymeric compound to a Mixture of the liquid crystal material and the photo-curable resin Generation of the disclosure lines in these elements prevented. Through the However, adding conventional polymeric compounds will make the pretilt increased angle of the liquid crystal material in the liquid crystal areas,  causing the brightness of the element in the absence of an electrical span voltage is reduced.

There was therefore the relationship between the structure of the polymeric compound formation and the orientation of the liquid crystal molecules at the interface examined between the liquid crystal material and the polymer wall, a compound was found with which a liquid crystal Can form display element that does not generate any disclosure lines and also in Absence of an electrical voltage has bright display properties.

The invention therefore relates to the polymeric compound according to claim 1 and use as a liquid crystal display element according to claim 4, such as it is stated in the claims.

According to one 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 embodiment, in the general formula (I) either A or B represents a hydrogen atom.

According to a preferred embodiment, in 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)

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 compound of the general formula (I), Y ₁ and Y _{2 represent} a fluorine atom.

The liquid crystal display element according to the invention comprises a pair of sub straten, which are opposed to each other to form a gap and a liquid crystal layer placed in 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 molecules is either statistical, radial, concentric or spiral.  

According to a preferred embodiment, the substrates are with an orien 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.

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 the orientation layer and the liquid crystal region is formed, to be humiliated. However, if the polymeric compound of the invention is contained in the polymer layer, the ability to transfer the Orientation-limiting force of the orientation layer on the liquid crystal molecules inside the liquid crystal areas also in the polymer layer enables, thereby the orientation of the liquid crystal molecules as Consequence of the presence of a material with a structure similar to that of the Liquid crystal material is stabilized in the polymer layer.

If 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 become 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 controlled. 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 is maintained by the polymer wall receive. 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 the gravitational force, conventional liquid crystal Large-sized display elements arranged vertically below different thicknesses in the lower and in the upper area. This leads to a uneven display. Since the substrates of the liquid according to the invention crystal 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 find the liquid crystal molecules in the liquid crystal areas to orientate statistically, concentrically, radially or spirally under effective Mer exploitation of the phase separation between the liquid crystal material and the poly consisting essentially of the polymeric polymer materials wall at the time of hardening of the liquid crystal composition settlement. Because the liquid crystals of the liquid crystal regions are axisymmetric oriented, shows the liquid crystal display thus obtained 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 according to the invention.
• 5. The liquid crystal display element according to the invention is for display facilities aimed at a person, such as typewriters, Suitable for personal computers, as well as for display devices that adapt themselves  judge a large number of people (especially those who are on one Desk is arranged, which is surrounded by 2 to 4 people), like lazy Information display facilities.

The drawings show:

FIG. 1a to 1c are enlarged views of the liquid crystal region to the invention OF INVENTION A liquid crystal display element;

Fig. 2 is a schematic representation that illustrates the viewing angle properties of an element in TN mode;

Fig. 3 is a schematic representation, which gives the disclination lines at the time of applying an electric voltage again;

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

Fig. 5 is an illustration of the photo mask described in Example 9;

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

Fig. 7a to 7f a series of graphs which illustrate the electro-optical properties (viewing angle characteristics) of the element produced according to Example 11, and

FIG. 8a to 8f a series of graphs representing the electro-optical properties (viewing angle characteristics) of an element in the 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

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, is produced, the orientation-limiting force of the orientation tends films on the liquid crystal molecules in general by forming a Polymer layer made of the polymeric polymer material between the orientie Formation layer and the liquid crystal region is formed to taper weaknesses. However, if the polymeric compound of the invention in the Polymer layer is included, the ability of the transfer of the Orientation-limiting force of the orientation layer on the liquid crystal molecules within the liquid crystal area in the polymer layer maintained, whereby the orientation of the liquid crystal molecules is stabilized. This is a consequence of the presence of a material with a structure similar 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), this will normally result reverse slope at the time of application of an electric voltage, disclosure lines d (see Fig. 3) are generated on the periphery of the liquid crystal region. However, by adding the polymeric compound of the present invention, the liquid crystal molecules are preinstalled on the substrate so that the formation of the disclination lines is controlled at the time of applying an electric voltage (which is believed to be a result of the fact that the liquid crystal molecules are oriented approximately at right angles when an electrical voltage is applied).

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 ₂ ) _m - or - (CH ₂ ) _n -, which connect the mesogenic group with the functional polymeric group, are capable of increasing the viewing angle properties of the liquid crystal display devices produced in this way influence.

In the formulas given above, m and n have values from 3 to 14 and more preferably from 4 to 7. If both m and n are 2, the polymeric compound is too reactive in practice. If the values of m and n exceed 14 each, the mesogenic sections appear on the Surfaces of the polymer wall and the polymer layer, so that the response speed is reduced, which is believed to be a result of The fact is that the mesogenic groups are oriented in the same way like the liquid crystal molecules. The longer the chain length of the connecting Groups, the smaller the amount of polymeric compound required for Achieving a limiting effect on the generation of the disclinations lines is necessary. At the same time, however, the angle of inclination is increased, which reduces the translucency of the cell. Therefore it is needed derlich that the amount and type of polymeric compound in the way selected to keep the disclination lines under control and an increase in the pre-tilt angle can 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 area and a polymer wall surrounding the liquid crystal area, the liquid crystal region and the polymer wall through the phases separation of a mixture of a liquid crystal material and a poly polymer material has been formed by the polymerization reaction, the following problems (a) to (d) arise:

Problems and the causes assumed for them

• a) Low response speed - dissolution of monomers of the poly material in the liquid crystal;  
• b) Generation of the hysteresis effect - strong anchoring of the liquid crystal Molecules on the polymer wall:
• c) High driver voltage - same cause as given under (b);
• d) light scattering 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 on 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 material. Both problems can be solved by using a fluorinated one polymeric compound can be overcome. Since it is assumed that the fluorinated 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 a lot number of polymerizable functional groups to the mesogenic group Liquid crystal properties are bound. 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 - (CH ₂ ) _m - or - (CH ₂ ) _n - which bind the above-described mesogenic group to the polymeric functional group are the same as for the above-described monofunctional compound however, preferably 12 or less. Above 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 an area showing a smaller amount of twisting as shown in Fig. 4 than when using the monofunctional with respect to the generation of disclosure lines 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 polar sator the liquid crystal molecules at the time of saturation voltage is approximately perpendicular to the substrate (if Δε <0),

• 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 Direction 45 ° from the polarization axis of the polarizer.

The cause of the problem (2) mentioned above is that the light entering from the polarization direction of the polarizer has either only a normal beam or only an extraordinary beam when passing through the refractive index ellipsoid of the liquid crystal layer while this Light incident at 45 ° from the polarization axis of the polarizer has both an ordinary beam and an extraordinary beam that passes through the refractive index ellipsoid of the liquid crystal layer. This causes the light to scatter or spread as a result of the elliptical polarization. It is therefore preferred that the delay through the liquid crystal layer is as small as possible so that no elliptical polarization can result. Since the transmittance T _{0 is} influenced by the delay through the liquid crystal layer in the absence of an electrical voltage, it is preferred in view of ensuring omnidirectional properties of the viewing angle properties and the brightness of the cell that the delay of the liquid crystal layer be 300 nm to 650 nm is. If the retardation is less than 300 nm, the cell will indicate darkness in the absence of an electrical voltage as a result of the absence of brightness. It is therefore preferred that the angle of rotation is 45 ° to 150 ° and in particular in the vicinity of 90 °, whereby the first minimum conditions are met, since the cell shows its greatest brightness at this 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 multiplicity of liquid crystal regions 20 and a polymer wall 21 surrounding the liquid crystal regions 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. A photomask 3 is arranged on one side of the cell, as shown in FIG. 5. A liquid crystal composition containing a liquid crystal material, a polymeric polymer material and at least one of the polymeric compounds described above is then introduced into the cell. The cell is then irradiated with ultraviolet radiation over the side with 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 surrounded by polymer walls composed of the polymeric polymer material and polymeric compounds in the regions 30 corresponding to the photomask described above, as is is shown in Fig. 6.

The polymeric polymeric materials used for the display described above element 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 Acrylates with long chain alkyl groups with three or more carbon atoms or a benzene ring including isobutyl acrylate, stearyl acrylate, Laury acrylate, isoamyl acrylate, n-butyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, 2-ethylhexyl acrylate, n-stearyl methacrylate, cyclohexyl methacrylate, Benzyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate. The light-curable resins also include polyfunctional resins which increase the physical strength of the polymer material, such as Bisphenol A di-methacrylate, bisphenol A diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, neopentyl diacrylate.

5. Driver methods

The liquid crystal display element prepared in this way can with 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 driving method according to the invention is not is particularly limited.

6. Substrate materials

The substrate materials to be used according to the invention include glass plates, plastic plates and the like, made of transparent hard substances have been produced, and substrates with a thin metal layer, Si substrates and the like made from non-transparent solids represents are. The substrates with a thin metal layer are for liquid crystal display elements of the reflection type are suitable.  

The plastic substrate is preferably made of a material that is visible Light not absorbed, including, for example, polyethylene terephthalate (PET), acrylic polymers, polystyrenes, polycarbonates and the like. When a Plastic substrate used, the ability of the polarization 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.

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 the general formula (I) in which A and B represent the same group is prepared in accordance with the following reaction scheme:

Synthesis route 3: The compound of the general formula (I) in which either A or B represent a hydrogen atom is prepared according to the following reaction scheme:

Synthesis route 4: The intermediate compound is prepared according to the following reaction scheme:

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

Synthesis route 1

The compounds represented by the general formulas (1), (4), (5), (6), (7) and (8) are commercially available. The compound of the general formula (3) in which Y ₁ and Y ₂ each represent hydrogen atoms or fluorine atoms are also commercially available.

The compound of general formula (1) is reacted with C ₄ H ₉ Li and then with B (OCH ₃ ) ₃ and hydrolyzed to form the compound of general formula (2), which is then oxidized with hydrogen peroxide to form 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 etherified with methoxymethyl chloride (MOM-Cl) to form the compound of general formula (13), which is then reacted with C ₄ H ₉ Li and then with B (OCH ₃ ) ₃ and then hydrolyzed becomes 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 reacted with magnesium (Mg) to form a Grignard reagent. The compound of general formula (15) can also be obtained by reacting the Grignard reagent with B (OCH ₃ ) 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 cleaved 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 Formation 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 the Compound of the general formula (12).

EXAMPLES

Examples 2, 3, 6, 9 to 11, 14 to 16, 18 and 19 represent the invention Examples of polymerizable compounds according to claims 1 to 4 or for liquid crystal display elements using such a compound The other examples serve to illustrate of synthesis and manufacturing processes.

The data for prints in mmHg should be converted as follows: 1 mmHg ent speaks 133.3 Pa.

The abbreviations used in the examples have the following meanings:

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

EXAMPLE 1

(a) 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:

100 g of 1,2-difluorobenzene and 350 ml of tetrahydrofuran (THF) are charged to a reactor under an argon stream, and 700 ml of a 1.6 MC ₄ are then added dropwise with stirring at a temperature of from -50 ° C. to -60 ° C. H ₉ Li (butyllithium) solution in hexane and stirred for 1 hour at the same temperature to form a solution. 175 g of trimethyl borate (CH ₃ O) ₃ B are then added dropwise and the mixture is stirred at room temperature for 1 hour.

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 (PPh ₃ ) ₄ , 210 ml of a solution of 33 g of 4-bromophenyl methoxymethyl ether, which was obtained in synthesis example (a) described above, are charged to a reactor under an argon stream Benzene, 135 ml of an aqueous 2 M Na ₂ CO ₃ solution and 120 ml of an ethanolic solution of 24 g of 2,3-difluorophenylboric acid obtained in synthesis step (b) described above, and the mixture is stirred under reflux for 6 hours The reaction solution is poured into water, extracted with toluene, washed with water, dried over anhydrous sodium sulfate, the solvent is evaporated, and the residue is distilled under reduced pressure to obtain 20.1 g (yield = 53.6%) 2,3-difluoro4 '- (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 6 N HCl solution and stirred 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 obtained.
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 3 N 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 over 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:

CH ₂ = CHCOO (CH ₂ ) ₆ Br

A reactor is charged with 30 g of 6-bromo-1-hexanol and 18.4 g of triethylamine and 500 ml of benzene and added dropwise while stirring and cooling with ice Solution of 16.5 g of acryloyl chloride in 200 ml of benzene. Stir during 3 Hours, the reaction solution washes with a 3 N HCl solution and then with Water, dries over anhydrous sodium sulfate, evaporates the solvent tel, purifies the residue by column chromatography over silica gel (elutions medium: toluene) and receives 25.4 g (yield = 65.1%) of 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 above-described synthesis step (d) of Example 1, 5.0 g of the 6-bromohexyl acrylate obtained in the above synthesis step (a), 5 , 4 g of K ₂ CO ₃ 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 recrystallized 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:

CH ₂ = CHCOO (CH ₂ ) ₁₂ Br

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 stage (b) of Example 2 is repeated the difference that instead of 5.0 g of 6-bromohexyl acrylate, 6.7 g of 12- Bromododecyl acrylate is used, and 2.1 g (yield = 24.1%) of 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 K ₂ CO ₃ and 300 ml of acetone and the mixture is stirred under 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) oxybromobenzene in 150 ml of benzene, 7.2 g of the 2,3-difluorophenyl obtained in step (b) of Example 1. boric acid, 68 ml of an aqueous 2 M Na ₂ CO ₃ solution and 1.0 g of Pd (PPh ₃ ) ₄ and stirred at reflux for 9 hours. The reaction solution is poured into water, extracted with toluene, washed with water, dried over anhydrous sodium sulfate, the solvent is evaporated, the residue is distilled under reduced pressure in a glass tube furnace, recrystallized from an ethanol / hexane mixture (1/1) and obtained 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 (PPh ₃ ) ₄ , a solution of 11.6 g of 1-bromo-2,3-difluorobenzene in 100 ml of benzene, 60 ml of an aqueous 2 M Na ₂ CO ₃ solution and a solution of 13.3 g of the 2,3-difluorophenyl boric acid obtained in synthesis step (b) of Example 1 in 100 ml of ethanol and stirred for 6 hours. The reaction solution is washed with a dilute hydrochloric acid solution and then with water, dried over anhydrous sodium sulfate, the solvent is evaporated, and the residue is distilled under reduced pressure to obtain 5.7 g (yield = 42%) 2,2 ', 3,3 '-Tetrafluorobiphenyl.

(b) Synthesis of the compound of the formula:

A reactor is charged under a stream of argon with 5.7 g of the 2,2 ', 3,3'-tetrafluorobiphenyl and 50 ml of tetra hydrofuran obtained in the above synthesis step (a), dropwise at a temperature of -50 ° C or less 38 ml of a 1.6 M solution of C ₄ H ₉ Li in hexane and stirred at this temperature for 2 hours, after which 10 g of trimethyl borate ((CH ₃ O) ₃ B) are added dropwise and gradually warmed to room temperature and stir 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 give a crystalline material, which is dissolved in 50 ml of tetrahydrofuran, after which 40 ml of a 10% aqueous H ₂ O ₂ solution is 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:

CH ₂ = CHCOO (CH ₂ ) ₈ Br

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 crude 2,2 ', 3,3'-tetrafluoro-4,4'-dihydroxybiphenyls obtained in the synthesis step (b) described above, 10.0 g of 8-acryloyloxy-1- bromoctane, which was obtained according to synthesis step (c) above, 7.8 g of K ₂ CO ₃ and 30 ml of acetone and stirred for 16 hours at reflux.

The reaction solution is filtered through a filter aid (high flow), and To luol to the filtrate, washed with water, dried over anhydrous sodium sulfate fat, evaporates the solvent, cleans the residue twice column-chro matographically 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

(a) 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'-dihy droxybiphenyl 3.6 g of the obtained in synthesis step (d) described above crude 2,3-difluoro-4,4'-dihydroxybiphenyl is used. 1.0 g (yield = 10.5%) 4,4'-bis [8- (acryloyloxy) octyloxy] -2,3-difluorobiphenyl. 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 one is added Solution of 66 g of the methoxymethyl obtained in synthesis step (a) above 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. After 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 (CH ₃ O ₃ ) B and 200 ml of tetrahydrofuran, after which the Grignard reagent prepared in the above-described manner is added dropwise with stirring at a temperature of 0 ° C. or lower, after which it is added and after warming to room temperature and then stirring 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 step (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 that obtained in synthesis step (c) above are obtained 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 that in the above Synthesis stage (d) 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 is 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 that in the above synthesis step (a) 2,3,3'-trifluoro-4,4'-bis (methoxymethoxy) biphenyl obtained. 14.7 g of crude 2,3,3'-trifluoro-4,4'-dihydroxybiphenyl are obtained.

(c) 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 above-obtained synthesis step (b) 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 (Examples 9 to 11 are examples of the invention) 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. The photomask 3 shown in FIG. 5 is applied to one side of the cell prepared in this way. 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, 13.3 given in Table 1 is injected using a capillary tube g of a liquid crystal material (ZLI-4792 from Merck, Inc.; Δn = 0.094) and 0.04 g of a photoinitiator (2,2-dimethoxy-1,2-diphenylethan-1-one).

TABLE 1

Applying an alternating voltage of ± 4 V to the transparent electrodes, the cell is irradiated for 8 minutes at 100 ° C. with parallel light from a high-pressure mercury lamp with a power of 10 mW / cm ² (the ultraviolet radiation will act in this way let there be 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 (Examples 14 to 16 are examples of the invention) Liquid crystal display elements using a bifunctional poly mer liquid crystal material

It is brought in a manner similar to that described in Examples 9 to 13 NEN cell produced a photomask in the in Examples 9 to 13th way described. Then you inject with the help of a capillary tube a 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 .; Δn = 0.094) and 0.04 g of one Photoinitiators (2,2-dimethoxy-1,2-diphenylethan-1-one) into the cell.

TABLE 3

The cell into which the mixture has been injected is then put on an electrical voltage in the same way as in Examples 9 to 13 described, irradiated with ultraviolet radiation to form a liquid crystal Form display element.

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 photo mask 3 shown in FIG. 5 is applied to 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 photo initiator (2,2-dimethoxy-1,2-diphenylethan-1-one) 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 is made using the spin coating process on 1.1 mm thick glass substrates, the transparent electrodes from 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 substrates produced in this way are over one 5 µm spacers attached to each other so that the rubbing directions in 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 (2,2-dimethoxy-1 , 2-diphenylethan-1-one) into the cell. Then, according to the procedure of Examples 9 to 13, a liquid crystal display element of TN mode (Twisted Nematic Mode) is prepared, the liquid crystal areas of which 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 is applied using a spin coating process on 1.1 mm thick glass substrates, the transparent electrodes from a mixture of indium oxide and tin oxide with a thickness of 50 nm (500 Å) (ITO electrodes) and rubs the material treatment with a nylon cloth. You fasten the two in this way manufactured substrates using a 9-µm spacer in the Way that the rubbing directions are 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, 13.3 used in Example 11 is injected using a capillary tube g of a liquid crystal material (ZLI-4792 manufactured by Merck, Inc .: the drilling angle of which has been set to 240 ° using a chiral material, S811) and 0.04 g of a photoinitiator (2,2-dimethoxy-1,2 -diphenylethan-1-one) into the cell. Subsequently, a liquid crystal display element of the STN mode is prepared according to the procedure of Examples 9 to 13 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 are 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 is applied using a spin coating process on 1.1 mm thick glass substrates with transparent electro from a mixture of indium oxide and tin oxide with a thickness of 50 nm (500 Å) (ITO electrodes) and subjects the layer to one Rubbing treatment with a nylon cloth. You fasten the two in this way manufactured substrates together using a 2-µm spacer such that the rubbing directions 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 Indu stries, 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 (2,2-dimethoxy-1,2-diphenylethane -1-on) into the cell. A liquid crystal display element of the FLC mode (orientation of the SSF type) with liquid crystal regions which are surrounded by a polymer wall is then prepared by the procedure described in Examples 9 to 13.

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.  

Comparative Example 2 (Submitted Later)

In the same manner as described in Example 9, a liquid crystal An Show element produced, with the exception that as a polymeric compound the structure shown below was used.

This compound corresponds to the compound used in Example 9, with except that the biphenyl group has no fluorine substituents. The driving voltage of the display element obtained was 2 V high forth than in the case of the display element according to Example 9. Because the smolder If the voltage of this display element was high, this display element could cannot be operated with the TFT driver method.

From this test result it follows that by a special combination of Characteristics, i.e. certain numerical values for the indices m and n as well Fluorine substitution of the biphenyl group, not foreseen according to the invention bare beneficial effects can be achieved.

Claims (8)

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
mean, however, A and B are not simultaneously hydrogen atoms, where X ₁ and X ₂ independently of one another are hydrogen atoms or methyl groups, m and n independently of one another are integers with values from 3 to 12 and

• a) when B represents a hydrogen atom,
  p has the value 0 or 1 and
  Y ₁ , Y ₂ , Y ₃ and Y ₄ independently of one another are hydrogen atoms or fluorine atoms with the proviso that at least one of the groups Y ₁ , Y ₂ , Y ₃ and Y _{4 represents} a fluorine atom, or
• b) when A is a hydrogen atom, Y ₁ and Y _{2 are} fluorine atoms and Y ₃ and Y _{4 are} independently hydrogen atoms or fluorine atoms, or
• c) if neither A nor B are hydrogen atoms, Y ₁ and Y _{2 are} fluorine atoms and Y ₃ and Y _{4 are} hydrogen atoms and p is 1.

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
X ₁ , X ₂ , m and n have the meanings given in claim 1. 3. Polymeric compound according to claim 1 of the general formula (I), characterized in that B represents a hydrogen atom and Y ₁ and Y _{2 are} fluorine atoms and Y ₃ and Y ₄ independently of one another are hydrogen atoms or fluorine atoms and p is 1. 4. Use of a polymeric compound according to at least one of the An claims 1 to 3 for a liquid crystal display element with a pair of one on opposite substrates spaced apart to form a Gap are arranged, a liquid crystal layer in the gap, wherein min at least one of the substrates is transparent and the liquid crystal layer is one Liquid crystal region and a polymer surrounding the liquid crystal region wall, wherein the liquid crystal layer is a liquid crystal material, a polymeric polymer material and a polymeric compound according to at least contains one of claims 1 to 3. 5. Use according to claim 4, wherein the liquid crystal region is liquid includes crystal molecules and the orientation of the liquid crystal molecules ent is neither statistical, radial, concentric or spiral. 6. Use according to claim 4, wherein an orientation film on the sub strat is arranged.   7. Use according to claim 4, wherein the liquid crystal region is liquid includes crystal molecules and the orientation of the liquid crystal molecules TN, STB, ECB or FLC orientation. 8. Use according to claim 4, wherein the polymer material is a light-curing resin.