JPH107617A - Polymerizable compound and liquid crystal display device using the same - Google Patents

Abstract

(57) [Summary] (With correction) [Problem] It does not generate a disclination line, has little deterioration in response speed and voltage-transmittance characteristics, is bright even when no voltage is applied, has high contrast, and has high intensity. Provided are a polymerizable compound for obtaining a liquid crystal display element having excellent heat resistance, and the liquid crystal display element. SOLUTION: The polymerizable compound of the general formula I. (X is hydrogen or a methyl group; l and m are independently an integer of 0 to 14; Y is a single bond; -COO-, -OCO- or -O-; n and p are independently an integer of 0 to 18 Q and s independently represent 0 or 1;
R ^A and R ^B are independently of formula II or III: However, when q = 1, p ≧ 2; when R ^A is the formula II,
R ^B is formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymerizable compound and a liquid crystal display device using the same. More specifically,
The present invention relates to a liquid crystal display device having a liquid crystal layer surrounded by a polymer (or a polymer wall). And a liquid crystal display device using the same.

[0002]

[Prior art]

(Liquid crystal display device using liquid crystal material and polymer material) (i) JP-T-58-501631 describes a polymer dispersion type liquid crystal display device having a liquid crystal material encapsulated with a polymer material. Have been. In this liquid crystal display element, utilizing the difference in the refractive index between the liquid crystal material and the polymer material, when no voltage is applied, a white turbid state due to scattering of liquid crystal molecules is displayed.
When a voltage is applied, a transparent state is displayed by a change in the refractive index of the liquid crystal molecules. JP-A-61-502128 discloses that a mixture of a liquid crystal composition and a photocurable resin is irradiated with ultraviolet rays to cause a three-dimensional phase separation between the liquid crystal material and the cured resin. A liquid crystal display device having a liquid crystal layer described above is described. These devices are basically liquid crystal display devices that electrically control the change of the scattering (white turbidity) -transmission (transparent) state of the incident light on the liquid crystal layer.

(Ii) Japanese Patent Application Laid-Open No. 1-269922 discloses that
The mixture of the liquid crystal composition and the photocurable resin (polymer material) is selectively irradiated with ultraviolet rays through a photomask (first step), and further irradiated with ultraviolet rays excluding the photomask (second step). A technique of selectively irradiating ultraviolet light to a region shielded by a photomask in the first-stage ultraviolet irradiation to form regions having different characteristics is described. The element thus obtained is basically a scattering element.

On the other hand, Japanese Patent Application Laid-Open No. Hei 5-257135 discloses that a substrate provided with an alignment film having an alignment regulating force is provided between substrates.
A liquid crystal element having a liquid crystal layer obtained by injecting a mixture of a liquid crystal composition and a photocurable resin and irradiating ultraviolet rays through a photomask provided on a substrate is described. This element is formed so that the picture pattern of the pattern of the photomask is reflected on the liquid crystal layer by utilizing the fact that the optical characteristics of the liquid crystal region are different between the inner portion and the outer portion where the photomask is disposed. . This device is a static drive liquid crystal device that controls the light transmittance of a liquid crystal layer by a voltage applied between electrodes provided on each substrate. Therefore, the configuration is different from that of a matrix driving liquid crystal element such as the element of the present invention described later.

(Principle of improving viewing angle characteristics of liquid crystal display element)
In order to improve the viewing angle characteristics of a liquid crystal display element, it is necessary to align liquid crystal molecules in at least three directions in a pixel (liquid crystal region). The principle of the improvement of the viewing angle characteristic will be described with reference to FIGS.

FIG. 27 is a schematic sectional view of a TN mode liquid crystal display element having no polymer wall, and FIG. 28 is a schematic sectional view of a liquid crystal display element having a liquid crystal region surrounded by the polymer wall. is there. The liquid crystal display element shown in FIG. 27 includes a substrate 1 provided to face the liquid crystal display, and a liquid crystal layer 10 interposed between the substrates 1 and 1. In the liquid crystal layer 10, the liquid crystal molecules are aligned in one direction. On the other hand, the liquid crystal display element shown in FIG. 28 has a substrate 1 disposed oppositely, and a liquid crystal layer 20 sandwiched between the substrates 1, 1. Area 2
It consists of 0. In the liquid crystal region 20, the liquid crystal molecules are aligned in an axially symmetric manner with respect to the axis X. 27 and 28, (a) shows a state in which a voltage is not applied to the liquid crystal layers 10 and 20, respectively, and (b) shows a state in which a voltage is applied to the liquid crystal layers 10 and 20, respectively. Are shown, and (c) shows the liquid crystal layer 1 respectively.
The state where a saturation voltage is applied to 0 and 20 is shown.

As can be seen from FIG. 27B, in the halftone display state, the refractive index of the liquid crystal molecules when the liquid crystal display element is viewed from the direction A, and the refractive index of the liquid crystal molecules when viewed from the direction B. Are different. Therefore, when viewed from the direction A, the direction B
The contrast is different from that seen from above. On the other hand, as can be seen from FIG. 28 (b), when the liquid crystal molecules are axially symmetrically aligned, the liquid crystal molecules in the halftone display state are viewed from the direction A and from the direction B. The apparent refractive indices are averaged, so that the contrast when viewed from both directions A and B becomes equal.

Thus, as shown in FIG. 28, the viewing angle characteristics of the liquid crystal display device in which the liquid crystal molecules are oriented in an axially symmetric manner are improved as compared with the viewing angle characteristics of the TN mode liquid crystal display device shown in FIG. Will be done.

(Specific examples of a device having a wide viewing angle mode) JP-A-4-338923 and JP-A-4-21
Japanese Patent No. 2928 describes a technique relating to a liquid crystal display element of a wide viewing angle mode in which polarizers orthogonal to each other are combined with the above-mentioned polymer dispersion type liquid crystal display cell.

Japanese Patent Application Laid-Open No. Hei 5-27242 discloses a method for improving the viewing angle characteristics of a non-scattering type liquid crystal display device using a polarizing plate by separating a liquid crystal and a polymer by phase separation from a mixture of the liquid crystal and a photocurable resin. A method of making a composite with a body is described. In this method, the alignment state of the liquid crystal domains becomes a random state due to the influence of the generated polymer. Therefore, since the rising directions of the liquid crystal molecules are different in the individual liquid crystal domains when a voltage is applied, the apparent refractive indices of the liquid crystal molecules viewed from each direction become equal, and the viewing angle characteristics in a halftone display state are improved.

JP-A-6-265902 and JP-A-6-324337 disclose a concentric or axially symmetric alignment process for each pixel of a substrate constituting a liquid crystal display cell to provide a wide field of view. A technique for manufacturing an angular mode liquid crystal display element is described. With these technologies,
It is important to control the alignment of liquid crystal molecules for each pixel, but the process is complicated and the controllability is extremely low.

Recently, the present inventors have disclosed in Japanese Patent Application Laid-Open No. 6-301.
No. 015 proposes a liquid crystal display device having improved viewing angle characteristics. This liquid crystal display element is manufactured by irradiating a liquid crystal display cell containing a liquid crystal composition and a photocurable resin with light through a photomask. In the manufactured liquid crystal display element, a liquid crystal region in which liquid crystal molecules are in an omnidirectional alignment state (axially symmetrical alignment) is formed in a pixel portion corresponding to a light-shielding region of the mask. A polymer wall made of a conductive resin is formed. In this liquid crystal display device, the liquid crystal molecules form an omnidirectional alignment state, and operate with the voltage response behavior as described with reference to FIG. 28, whereby the viewing angle characteristics are significantly improved.

FIG. 29 is a plan view of the liquid crystal display device shown in FIG. 28 when a voltage is applied. In the figure, the position where the photomask was provided at the time of device fabrication is indicated by a broken line 23. FIG.
As can be seen from FIG. 2, the liquid crystal region 20 is formed substantially reflecting the shape of the photomask. Thus, the liquid crystal region 20
Are oriented symmetrically with respect to the axis (the axis X perpendicular to the substrate surface shown in FIG. 28A), the liquid crystal molecule 20 is usually surrounded by a voltage when a voltage is applied. Disclination line 22 by reverse tilt
Occurs.

Then, the present inventors have succeeded in Japanese Patent Application No. Hei 6-132288 in order to improve disclination which occurs at the time of voltage application, which is a problem in the liquid crystal display element described above. It has been proposed to add a linear polymerizable compound having a liquid crystal-like skeleton to a mixture of a liquid crystal composition and a photocurable resin.

Further, the present inventors have developed an alkyl fluoride group such as a perfluoro group in order to solve the problems such as the response speed and the steepness of the voltage-transmittance characteristic which have been left as problems in the above invention. Japanese Patent Application No. 7-175264 has proposed an invention relating to a material composition in which the introduced linear polymerizable compound having a liquid crystal-like skeleton is added as a resin system, and a liquid crystal device manufactured using the material composition.

[0016]

In the liquid crystal display device described above, at the interface between the polymer wall and the liquid crystal region,
There is a problem that disclination due to reverse tilt of liquid crystal molecules occurs. Since this disclination is displayed as a bright line, the display characteristics in the black state deteriorate.

On the other hand, in order to suppress the occurrence of disclination, the following two problems have been observed in a liquid crystal display device using a polymerizable compound as proposed above. First, there is a problem that the pretilt of the liquid crystal molecules in the liquid crystal region increases, and the brightness decreases when no voltage is applied. Second, the response speed of the liquid crystal element deteriorates due to the interaction between the polymer-liquid crystal composite layer and the interface between the polymer wall and the liquid crystal region, and the voltage-
Problems such as deterioration of threshold characteristics and steepness of transmittance characteristics are recognized.

Further, in the above-mentioned liquid crystal display device, a method of controlling the alignment of liquid crystal for obtaining omnidirectional alignment in a pixel necessary for improving the viewing angle characteristics, and a method of controlling scattering occurring at an interface between liquid crystal and a polymer. The problem is how to prevent a decrease in contrast due to depolarization due to the light. In order to suppress the scattering occurring at the interface between the liquid crystal and the polymer, a method of reducing the interface between the liquid crystal and the polymer in the pixel can be considered. However, with the conventional method, it is extremely difficult to control the size, formation position, and the like of the liquid crystal droplet generated in the three-dimensional polymer matrix.

In order to solve these problems, it is important not only to suppress the occurrence of disclination, but also to select a polymerizable compound that does not deteriorate the response speed and the voltage-transmittance characteristic. In addition, it is useful to form at least one liquid crystal droplet in a pixel. That is, in order to realize a liquid crystal display device in which the conventional liquid crystal display mode is quasi-solidified, it is necessary to solve the above-mentioned problems of controlling the liquid crystal alignment and suppressing the scattering intensity both or independently.

Furthermore, the conventional linear polymerizable compound having a liquid crystal-like skeleton has the following problems: (1) Due to its reactivity, unreacted compounds remain and the characteristics of the liquid crystal display element deteriorate. (2) the strength (eg, pressure resistance, impact resistance) and heat resistance of the formed polymer (wall) are insufficient due to the molecular structure of the polymerizable compound, and as a result, the liquid crystal display Problems such as insufficient strength and heat resistance of the element;

[0021]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a device which does not generate a disclination line, has a response speed and a voltage-transmittance. Little degradation of rate characteristics,
Provided is a polymerizable compound that can provide a liquid crystal display element that is bright even when no voltage is applied, has high contrast, and is excellent in strength (for example, pressure resistance and impact resistance) and heat resistance, and a liquid crystal display element such as this. Is to do.

As a result of intensive studies, the present inventors have found that by using a polyfunctional compound having a liquid crystal-like skeleton and having a branched polymerizable active group, the disclination line is not generated and the response is improved. A liquid crystal display device which has little deterioration in speed and voltage-transmittance characteristics, is bright even when no voltage is applied, has high contrast, and is excellent in strength (for example, pressure resistance, impact resistance) and heat resistance. And completed the present invention.

The polymerizable compound of the present invention is a compound represented by the following formula (I):

[0024]

Embedded image

Wherein X is a hydrogen atom or a methyl group; l and m are each independently an integer from 0 to 14; Y is a single bond, -COO-, -OCO-, or N and p are each independently an integer from 0 to 18; q and s are each independently 0 or 1; R ^A and R ^B are each independently And represented by formula (II) or formula (III):

[0026]

Embedded image

However, when q = 1, p ≧ 2; R ^A
When is represented by the formula (II), R ^B is represented by formula (II).

In a preferred embodiment, in the above formula (I), n + p ≦ 18.

In a preferred embodiment, in the above formula (I), n + p ≦ 18 and s = 0.

In a preferred embodiment, in the above formula (I), n + p ≦ 18 and s = 1.

The liquid crystal display device of the present invention is a liquid crystal display device in which a liquid crystal layer having a polymer and a liquid crystal region surrounded by the polymer is sandwiched between a pair of substrates. , Formed from a polymerization precursor containing at least the above polymerizable compound.

In a preferred embodiment, the alignment state of the liquid crystal molecules in the liquid crystal region is axially symmetric, radial or concentric alignment, spiral alignment, or random alignment.

[0033] In a preferred embodiment, the liquid crystal display element includes an insulating film on the substrate for regulating an alignment state of liquid crystal molecules.

In a preferred embodiment, the liquid crystal display element further comprises an insulating alignment film on the substrate for realizing uniform uniaxial alignment of liquid crystal molecules corresponding to the liquid crystal region. And the alignment state of the liquid crystal region and the overall configuration of the device are TN, STN, ECB, and SSF.
The arrangement is suitable for the LC mode.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION In this specification, "a liquid crystal layer having a polymer and a liquid crystal region surrounded by the polymer" means that the liquid crystal region is completely surrounded by a polymer (polymer) or covered. A liquid crystal layer having a separated liquid crystal region, a liquid crystal layer having a liquid crystal region separated by a columnar or wall-shaped polymer, or a liquid crystal layer having a liquid crystal region separated by a three-dimensional network formed by a polymer, or the like. A liquid crystal layer having a structure in which liquid crystal molecules in a liquid crystal region are separated from a polymer.

(Polymerizable compound) The polymerizable compound of the present invention comprises
It is a polyfunctional compound having a liquid crystal-like skeleton and having a branched polymerizable active group. The polyfunctional compound of the present invention easily forms a three-dimensional network structure and has excellent reactivity. Therefore, the polyfunctional compound of the present invention maintains the properties of the conventional monofunctional “polymerizable compound having a liquid crystal-like skeleton”, and at the same time, reduces the deterioration of the characteristics of the liquid crystal display device due to the unreacted compound. And the glass transition temperature of the polymer
The greatest feature is that the characteristics of the polyfunctional compound such as improving (Tg) can be simultaneously realized.

The structure of the polymerizable compound of the present invention is not particularly limited, but preferably has the structure represented by the above formula (I). This polymerizable compound has a structure in which a polymerization active group is branched and introduced into a molecule, and is bonded to a mesogen group having a structure similar to liquid crystal via a linking group. In the above formula (I), X is a hydrogen atom or a methyl group; l and m are each independently an integer of 0 to 14; Y is a single bond, -COO-, -OCO-, Or -O-; n and p are each independently an integer from 0 to 18; q and s are each independently 0 or 1; R ^A and R ^B are each independently And the above equation (I
It is represented by I) or the above formula (III). However, when q = 1, be a p ≧ 2; when R ^A is represented by formula (II), R ^B is represented by the formula (II).

Since the polymerizable compound of the present invention has a mesogen skeleton having a structure similar to liquid crystal in the molecule, a polymer formed from a monomer containing the polymerizable compound of the present invention has a mesogen group introduced therein. Formed as a polymer. As a result, the alignment regulating force of the alignment film can reach the liquid crystal molecules in the liquid crystal region, and the alignment state of the liquid crystal molecules is stabilized. Further, since pretilt is generated in the liquid crystal molecules, the generation of disclination lines when a voltage is applied is suppressed. In addition, when using a compound having a cyclohexyl ring introduced as a part of a mesogen group,
The refractive index of the polymer (polymer) becomes equal to or close to the value of the ordinary light refractive index (n _o ) of the liquid crystal material to be used, and the liquid crystal cell is disposed between two polarizers arranged orthogonally (crossed Nicols). When the voltage is applied, the light transmittance decreases at the interface between the liquid crystal and the polymer due to the refractive index matching. Due to these factors, when a voltage is applied, the black state display becomes good, and a high-contrast display can be realized.

The polymerizable compound of the present invention is a polyfunctional compound having a liquid crystal-like skeleton and having a branched polymerizable active group. The effect of the polymerizable compound having a structure similar to the liquid crystal will be described in detail below.

In general, a liquid crystal display device produced by a phase separation accompanied by a polymerization reaction from a mixture of a liquid crystal material and a polymerizable resin material has problems as shown in Table 1.

[0041]

[Table 1]

The causes of the above problems are mainly that the anchoring strength of the liquid crystal molecules to the polymer wall is high and that the compatibility between the polymer material and the liquid crystal material is good. To solve these problems, it is effective to use a fluorinated polymerizable compound. Since the polymer portion formed by the fluorinated polymerizable compound has a different surface free energy from the non-fluorinated polymer portion, the polymer portion appears on the polymer wall and the surface of the polymer layer. As a result, the surface free energy of the polymer decreases and the anchoring strength between the polymer layer and the liquid crystal molecules decreases, so that the alignment state of the liquid crystal can be stabilized. Alternatively, since the fluorinated resin material and the liquid crystal material have different surface free energies, the compatibility between the polymer material and the liquid crystal material is reduced. Therefore, it is also effective to partially fluorinate the mesogen group as defined in the present invention.

Moreover, the polymerizable compound of the present invention is a polyfunctional compound having a liquid crystal-like skeleton and having a branched polymerizable active group. The polyfunctional compound of the present invention easily forms a three-dimensional network structure and has excellent reactivity. Therefore, the polyfunctional compound of the present invention maintains the properties of the conventional monofunctional “polymerizable compound having a liquid crystal-like skeleton”, and at the same time, reduces the deterioration of the characteristics of the liquid crystal display device due to the unreacted compound. And the glass transition temperature (Tg) of the polymer
The greatest feature is that the characteristics of the polyfunctional compound such as improving the properties can be simultaneously realized. Therefore, the display characteristics and strength (eg, pressure resistance, heat resistance) of the liquid crystal display element
This is extremely effective from the point of view.

The mesogen skeleton of the polymerizable compound of the present invention and the ethylenically unsaturated group serving as a polymerization active group are linked via a linking group. As the linking group,-(CH ₂ ) _l -[(CH ₂ ) _m ] CH
_{- (CH2) n -Y- (CH} 2) p - (O) q - skeleton having a branched structure such as is preferred. l and m are each independently an integer of 0 to 14, preferably an integer of 0 to 12. Y is a single bond,
-COO-, -OCO-, or -O-. Preferably, it is a single bond or -COO-. n and p are each independently an integer of 0 to 18, preferably an integer of 0 to 12. Preferably, n + p ≦ 18. q is an integer of 0 or 1. If l or m is greater than 14,
Alternatively, when n or p is larger than 18, the mesogen portion protrudes from the surface of the polymer constituting the polymer wall surrounding the liquid crystal region, thereby deteriorating the response speed of the liquid crystal molecules. Further, the effect of suppressing the generation of disclination lines tends to be exerted with a small amount as the chain length increases, but the pretilt increases to decrease the cell transmittance. Therefore, it is important to control the disclination line and to select the amount of addition and the type of compound so that the pretilt does not increase.

When a polymer constituting the polymer wall surrounding the liquid crystal region is obtained by using the polymerizable compound of the present invention, the polymerizable compound of the present invention may be homopolymerized or co-polymerized with another polymerizable monomer. It can be polymerized. As other polymerizable monomers, acrylic acid having an alkyl group or a benzene ring, monofunctional monomers including acrylates and methacrylates, and bifunctional or higher polyfunctional monomers, for example, ,
Bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate,
Examples thereof include 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, and R-684 (manufactured by Nippon Kayaku Co., Ltd.).

When copolymerized with another polymerizable monomer,
The polymerizable compound of the present invention has a total monomer weight of preferably 3%.
% To 60% by weight, more preferably 3% to 40% by weight
At a rate of

(Method for synthesizing polymerizable compound of the present invention)
The method for synthesizing the polymerizable compound specified in the present invention will be specifically described. The synthetic route described below is an example,
The present invention is not limited by these.

(Synthesis Route 1) In the above formula (I), Y
Is a single bond, R ^A is represented by the formula (II), and s =
The case of 0 will be described. 1 and 2 schematically show synthesis route 1.

L, m ≠ 1: a commercially available compound (1)
Compound (3) obtained by subjecting commercially available compound (2) to a compound (3) obtained by benzylation under alkaline conditions
(4) is obtained. Compound (7) is obtained by condensing compound (4) and benzylated compound (6) of compound (5) in the same manner. The compound (7) is decarboxylated with lithium chloride and dimethyl sulfoxide to obtain a compound (8), and then reduced with lithium aluminum hydroxide or the like to obtain a compound (9). Compound (9) is brominated with carbon tetrabromide to give compound
After (10), compound (11) is obtained by reacting with sodium iodide.

Compound (13) is obtained by reacting commercially available compound (12) with butyl lithium and trimethyl borate and hydrolyzing with dilute sulfuric acid. Compound (13) and a commercially available compound
Compound (15) is obtained by a palladium-catalyzed coupling reaction with (14). On the other hand, compound (17) is obtained by reacting compound (16) with benzyl chloride. Compound (18) is obtained by subjecting compound (17) and compound (15) to an etherification reaction under alkaline conditions. Compound (18) is debenzylated with hydrogen gas under a palladium catalyst to give compound (19), and then oxidized with pyridinium chlorochromate (PCC) to give compound (20).

Compound (22) is obtained by subjecting commercially available compound (21) and compound (13) to a coupling reaction in the presence of a palladium catalyst. After preparing a Grignard reagent for compound (22), the compound (23) is obtained by coupling reaction with compound (17) under a copper catalyst. Compound (23)
Is debenzylated with hydrogen gas under a palladium (Pd) catalyst to give compound (24), and then oxidized with PCC to give compound (25).

Compound (27) is obtained by a coupling reaction between commercially available compound (26) and compound (13) under a Pd catalyst.

Compound (11) and compounds (20), (25) and (2)
By Wittig reaction with 7), compounds (28) and (29), respectively
And (30) are obtained. On the other hand, compound (31) is obtained by reacting compound (10) with a Grignard reagent of compound (22) under a copper catalyst. Compounds (28), (29), (30) and
Compound (32) is obtained by adding hydrogen gas to each of (31) under a Pd catalyst. Compound (33) is obtained by reacting compound (32) with acrylic acid chloride or methacrylic acid chloride. Compound (33) is also a dehydration condensation of compound (32) with acrylic acid or methacrylic acid with dicyclohexylcarbodiimide (DCC),
It can also be obtained by the Mitsunobu reaction.

When l = m = 1: Compound (15) and Compound (34)
A compound (35) is obtained by the Mitsunobu reaction with

The benzyl compound (36) of the compound (34) and the compound (2
The compound (37) is obtained by subjecting the Grignard reagent of 2) to a coupling reaction under a copper catalyst, and then debenzylation with hydrogen gas under a Pd catalyst to obtain a compound (38). Compound (39) is obtained by brominating compound (38) with carbon tetrabromide.

The compound (41) is obtained by the coupling reaction between the commercially available compound (40) and the compound (13). Compound (41)
Is reduced with lithium borohydride to obtain a compound (42), and then brominated with carbon tetrabromide, phosphorus tribromide or the like to obtain a compound (43).

Compound (44) is obtained by subjecting each of compounds (35), (39) and (43) to a condensation reaction with compound (1) under alkaline conditions. The compound (44) is reduced with lithium borohydride to obtain a compound (45), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (46). Compound (46) is also compound (4
It can also be obtained by dehydration-condensation of 5) with acrylic acid or methacrylic acid by DCC and Mitsunobu reaction.

(Synthetic route 2) In the above formula (I), Y
Is a single bond, R ^A is represented by formula (III), and s =
The case of 0 will be described. 3 and 4 schematically show Synthesis Route 2.

L, m ≠ 1: butyl lithium is allowed to act on compound (12) to form a lithium salt, and then a commercially available compound
Compound (48) is obtained by condensation with (47). Compound (48)
Is dehydrated with p-toluenesulfonic acid to give compound (4
9) is obtained. Compound (49) is hydrogenated under a Pd catalyst to give compound (50), and then deprotected under acidic conditions to give compound (51). The compound (52) is obtained by reducing the compound (51) with sodium borohydride and purifying the compound by recrystallization, column chromatography and the like. Compound (53) is obtained by an etherification reaction of compound (52) with compound (17) under alkaline conditions. Compound (53) was converted to Pd
Compound (54) is obtained by hydrogenation under a catalyst,
Further, compound (55) is obtained by oxidation with PCC.

The compound (51) is reacted with (methoxymethyl) triphenylphosphonium chloride to give a compound (56), which is then hydrolyzed under acidic conditions and isomerized under alkaline conditions to give the compound (56). 57) is obtained. Compound
(57) and a compound obtained by benzylation of compound (58)
Compound (60) is obtained by Wittig reaction with (59). Compound (60) is hydrogenated under a Pd catalyst to obtain compound (61), and then oxidized with PCC to obtain compound (62).

The compound (57) is reduced with sodium borohydride to give a compound (63), and then brominated with carbon tetrabromide to give a compound (64). Compound (65) is obtained by cyanating compound (64) with sodium cyanide.
Compound (65) is hydrolyzed under alkaline conditions to give carboxylic acid
After converting into [Compound (66)], the mixture is heated in methanol under acidic conditions to obtain Compound (67). Reduction of compound (67) with isobutylaluminum hydride (DIBAH) gives compound (68). Compound (68) is also obtained by reducing compound (67) with lithium borohydride to obtain compound (82),
It can also be obtained by oxidizing with PCC.

Compound (11) and compounds (55), (62), (68),
Wittig reaction with (57) and (51) gives compounds (69), (70), (71), (72) and (73), respectively. These are hydrogenated under a Pd catalyst to obtain a compound (74), and then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (75). Compound (75)
Can also be obtained by the dehydration condensation of compound (74) with acrylic acid or methacrylic acid by DCC, and the Mitsunobu reaction.

When l = m = 1: Compound (52) and Compound (36)
Compound (7)
6) is obtained. Compound (76) is compounded by a hydrogenation reaction.
After converting to (77), the compound is brominated with carbon tetrabromide or the like to obtain a compound (78). On the other hand, a compound (79) is obtained by a Wittig reaction between the compound (57) and the compound (17). Compound (79)
Is reacted with hydrogen gas under a Pd catalyst to give a compound (80), and then brominated with carbon tetrabromide or the like to give a compound (81).

The compound (67) is reduced to a compound (82), which is similarly brominated to give a compound (83).

Compound (84) is obtained by the condensation reaction of each of compounds (78), (81), (83) and (64) with compound (1) under alkaline conditions. The compound (84) is reduced with lithium borohydride to give a compound (85), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (86). Compound (86) is also a DC of compound (85) with acrylic acid or methacrylic acid.
It can also be obtained by dehydration condensation with C and Mitsunobu reaction.

(Synthesis Route 3) In the above formula (I), Y
Is —COO—, R ^A is represented by the formula (II), and s = 0
The case will be described. FIG. 5 schematically shows synthesis route 3.

L, m ≠ 1: Compound (87) is obtained by cyanating compound (10) with sodium cyanide. Hydrolysis of compound (87) under alkaline conditions gives compound (88).

The compound (89) can be obtained by protecting the hydroxyl group of the compound (34) with 3,4-dihydro-2H-pyran (THP). After preparing a Grignard reagent for compound (89), a coupling reaction with compound (10) is performed under a copper catalyst to obtain compound (90). Compound (91) was obtained by removing the protecting group under acidic conditions, and then oxidized with PCC to give compound (91).
(92) is obtained. Furthermore, compound (93) is obtained by oxidation with potassium permanganate or the like.

The compound (94) is obtained by an etherification reaction between the compound (15) and the compound (36). Compound (94) was debenzylated with hydrogen gas under a Pd catalyst to give compound (9).
5) is obtained.

Compound (96) is obtained by alkali hydrolysis of compound (8).

After deriving each of the compounds (96), (88) and (93) to an acid chloride, an esterification reaction is performed with each of the compounds (15), (42), (38) and (95). Yields compound (97). Compounds (96), (88) and
Each of (93) and compounds (15), (42), (38) and (95)
Dicyclohexylcarbodiimide (DCC) with each of
Compound (97) or by the Mitsunobu reaction
Can be obtained. After debenzylation of the compound (97) with hydrogen gas to obtain a compound (98), the compound (9) is treated with acrylic acid chloride or methacrylic acid chloride.
9) is obtained. Compound (99) can also be obtained by dehydration-condensation of compound (98) with acrylic acid or methacrylic acid by DCC or Mitsunobu reaction.

(Synthesis Route 4) In the above formula (I), Y
Is —COO—, R ^A is represented by formula (III), and s =
The case of 0 will be described. FIG. 6 schematically shows synthesis route 4.

L, when m ≠ 1: Compounds (96), (88) and (93) are each converted to an acid chloride, and then
By subjecting each of (52), (63), (82), (77) and (80) to an esterification reaction, compound (100) is obtained. Compounds (96), (88) and (93), and the compound
Compound (100) can also be obtained by condensation with each of (52), (63), (82), (77) and (80) using dicyclohexylcarbodiimide (DCC) or Mitsunobu reaction. The compound (100) is debenzylated with hydrogen gas to obtain a compound (101), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (102). Compound (102) can also be obtained by subjecting compound (101) and acrylic acid or methacrylic acid to dehydration condensation by DCC and Mitsunobu reaction.

(Synthesis Route 5) In the above formula (I), Y
Is -OCO-, R ^A is represented by the formula (II), and s = 0
The case will be described. FIG. 7 schematically shows synthesis route 5.

L, when m ≠ 1: a compound obtained by protecting one hydroxyl group of a commercially available compound (103) with a benzyl group
(104) is obtained. Compound (104) is oxidized with PCC to give compound
The compound (106) is obtained by reacting the compound (6) with a Grignard reagent. Also, l = m
In the case of the above, the Grignard reagent of the compound (3) or the compound (6) is allowed to act on the commercially available compound (107), followed by treatment with an acid to obtain the compound (108).

Compound (88) is converted to lithium aluminum hydride
Compound (109) is obtained by reduction with (LAH).

Compound (111) is obtained by a copper-catalyzed coupling reaction between compound (10) in which the hydroxyl group of compound (16) is protected with THP and compound (10), and the protecting group is removed under acidic conditions. Yields compound (112).

Compound (113) is obtained by subjecting compound (41) to alkaline hydrolysis.

A compound (11) in which compound (114) is protected with benzyl
Compound (116) is obtained by the coupling reaction of 5) with Grignard reagent of compound (22). Compound (116) is hydrogenated to remove the protecting group [Compound (117)], oxidized with PCC to obtain Compound (118), and then oxidized with potassium permanganate or the like to give Compound (119). can get. After the compound (120) was obtained by an etherification reaction of the compound (115) and the compound (15), the benzyl group was removed by hydrogenation [Compound (121)], and P
Compound (122) is obtained by oxidation with CC. The compound (123) is obtained by oxidizing the compound (122) with potassium permanganate or the like.

After deriving each of the compounds (113), (119) and (123) into an acid chloride, the compounds (106), (108),
Compound (124) is obtained by performing an esterification reaction with each of (9), (109) and (112). Also, compounds
(113), each of (119) and (123), and compound (106),
(108), (9), condensation with dicyclohexylcarbodiimide (DCC) with each of (109) and (112), or
Compound (124) can also be obtained by Mitsunobu reaction. Compound
After debenzylation of (124) with hydrogen gas to obtain compound (125), compound (126) is obtained by reacting acrylic acid chloride or methacrylic acid chloride. Compound (126) can also be obtained by dehydration-condensation of compound (125) with acrylic acid or methacrylic acid by DCC, and Mitsunobu reaction.

(Synthesis Route 6) In the above formula (I), Y
Is —OCO—, R ^A is represented by formula (III), and s =
The case of 0 will be described. FIG. 8 schematically shows synthesis route 6.

When l and m ≠ 1: Compound (127) is obtained by oxidizing compound (57) with potassium permanganate or the like. The compound (128) is obtained by a Wittig reaction between the compound (57) and the compound (36), and the compound (129) is obtained by hydrogenation under a Pd catalyst. Compound (129) is oxidized with PCC [compound (130)], and further oxidized with potassium permanganate or the like to obtain compound (131).

Compound (132) is obtained by etherification of compound (52) with compound (115) under alkaline conditions. Compound by debenzylation of compound (132) by hydrogenation
(133) is obtained. The compound (134) is obtained by subjecting the compound (133) to PCC oxidation, and the compound (135) is obtained by further oxidizing the compound (133) with potassium permanganate.

After deriving each of the compounds (127), (66), (131) and (135) into an acid chloride, the compound (106),
By subjecting each of (108), (9), (109) and (112) to an esterification reaction, compound (136) is obtained. Also,
Compounds (127), (66), (131) and (135),
Compound (136) can also be obtained by condensation with each of compounds (106), (108), (9), (109) and (112) by dicyclohexylcarbodiimide (DCC) or Mitsunobu reaction. The compound (136) is debenzylated with hydrogen gas to obtain a compound (137), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (13).
8) is obtained. Compound (138) can also be obtained by dehydration-condensation of compound (137) with acrylic acid or methacrylic acid by DCC, or a Mitsunobu reaction.

(Synthesis Route 7) In the above formula (I), Y
Is -O-, R ^A is represented by the formula (II), and s = 0. FIG. 9 schematically shows the synthesis route 7.

L, when m ≠ 1: Compounds (109) and (11)
Bromination with carbon tetrabromide in 2) gives compounds (139) and (140), respectively. Compounds (106), (108),
(9), each of (109) and (112), and compounds (43) and (3
By etherification reaction with each of 9) and (35) or with each of compounds (10), (139) and (140),
An etherification reaction with each of compounds (15), (42), (38) and (95) gives compound (141). Further, compound (141) is obtained by adding p- to compounds (106), (108), (9), (109) and (112) in place of compounds (10), (139) and (140).
It can also be obtained by performing an etherification reaction using a tosylate obtained by the action of toluenesulfonic acid chloride. The compound (141) is hydrogenated in the presence of a Pd catalyst to give the compound (142). The compound (143) is obtained by further reacting acrylic acid chloride or methacrylic acid chloride. Compound (143) is also
It can also be obtained by the dehydration condensation of compound (142) with acrylic acid or methacrylic acid by DCC or Mitsunobu reaction.

(Synthesis Route 8) In the above formula (I), Y
Is -O-, R ^A is represented by formula (III), and s = 0
The case will be described. FIG. 10 schematically shows the synthesis route 8.

When 1, m ≠ 1: Compounds (106), (108),
(9), each of (109) and (112) and compounds (64), (8
3), by an etherification reaction with each of (81) and (78), or with each of compounds (10), (139) and (140), and compounds (52), (63), (82), The compound (144) is obtained by an etherification reaction with each of (80) and (77). In addition, compound (144) includes compounds (10), (139) and (1)
Compound (106), (108), (9), (109) and (112) were subjected to etherification reaction using a tosylate obtained by reacting p-toluenesulfonic acid chloride instead of (40). Can also be obtained. Compound (145) is hydrogenated under a Pd catalyst to obtain compound (145).
The compound (146) is obtained by reacting acrylic acid chloride or methacrylic acid chloride. Compound
(146) can also be obtained by dehydration-condensation of compound (145) with acrylic acid or methacrylic acid by DCC or Mitsunobu reaction.

(Synthesis Route 9) In the above formula (I), Y
Is a single bond, and R ^A and R ^B are represented by the formula (II). 11 and 12 schematically show the synthesis route 9.

L, m ≠ 1: Compound (148) is obtained by the coupling reaction between commercially available compound (147) and compound (13). Compound (149) is obtained by etherifying compound (148) and compound (17) under alkaline conditions. The compound (149) is debenzylated with hydrogen gas to give the compound (150), and further oxidized with PCC to give the compound (151).

Compound (152) is obtained by reacting trimethyl borate with the Grignard reagent of compound (22) and hydrolyzing with dilute sulfuric acid. Compound (153) is obtained by the coupling reaction between compound (152) and compound (21). Compound
Compound (154) is obtained by a copper-catalyzed coupling reaction between the Grignard reagent of (153) and compound (17). Compound (154) is hydrogenated to remove the benzyl group to give compound (155), and further oxidized with PCC to give compound (156).

The compound (157) is obtained by a coupling reaction between the compound (26) and the compound (152) under the Pd catalyst.

Compound (11), compounds (151), (156) and
By Wittig reaction with (157), compound (158),
(159) and (160) are obtained. On the other hand, the compound (161) is obtained by a coupling reaction between the Grignard reagent of the compound (153) and the compound (10). Compounds (158), (159), (160)
Compound (162) is obtained by hydrogenating (161) and (161) in the presence of a Pd catalyst, and compound (163) is obtained by reacting acrylic acid chloride or methacrylic acid chloride. Compound (163) can also be compound (16
It can also be obtained by dehydration condensation of DCC with 2) and acrylic acid or methacrylic acid, and Mitsunobu reaction.

When l = m = 1: Compound (148) and Compound
The compound (164) is obtained by Mitsunobu reaction with (34).

Grignard reagent of compound (153) and compound
Compound (165) is obtained by a coupling reaction with (36), and the compound is obtained by hydrogenation under a Pd catalyst.
(166) is obtained. Compound (167) is obtained by brominating compound (166) with carbon tetrabromide. On the other hand, the compound
Compound (168) is obtained by the coupling reaction between (152) and compound (40), and further reduced by lithium borohydride to obtain compound (169). Compound (169)
Is brominated with hydrobromic acid or phosphorus tribromide to give compound (170).

Compound (171) is obtained by condensation reaction of each of compounds (164), (167) and (170) with compound (1) under alkaline conditions. Compound (171) is reduced with lithium borohydride to give compound (172), which is further esterified with acrylic acid chloride or methacrylic acid chloride to give compound (17)
3) is obtained. Compound (173) can also be obtained by subjecting compound (172) and acrylic acid or methacrylic acid to dehydration condensation by DCC and Mitsunobu reaction.

(Synthetic route 10) In the above formula (I),
Y = single bond, R ^A is represented by formula (III), and R
^{The case where B} is represented by the formula (II) or (III) will be described. 13 and 14 schematically show the synthesis route 10.

L, m ≠ 1: Compound (175) is obtained by oxidizing compound (174) with sodium dichromate. The compound (176) is obtained by protecting one oxo group of the compound (175) with ethylene glycol, and the compound (177) is obtained by condensing a lithium salt of the compound (12). By dehydrating the compound (177) with p-toluenesulfonic acid, the compound (178) is obtained. Compound (178) is hydrogenated in the presence of a Pd catalyst to give compound (179). Further, removal of the protecting group under acidic conditions gives compound (180).

The compound (180) is reduced with sodium borohydride, and the trans form is isolated by recrystallization or column chromatography to obtain the compound (181).
Compound (182) is obtained by condensation of compound (47) with Grignard reagent of compound (22). Compound (177) to compound (1
81) to obtain compound (1) from compound (182).
86) is obtained.

The etherification reaction of the compounds (181) and (186) with the compound (17) gives the compound (187). Further, the compound (189) is obtained by debenzylation and PCC oxidation. Can be

Compounds (180) and (185) are reacted with (methoxymethyl) triphenylphosphonium chloride to give compound (190), which is then hydrolyzed under acidic conditions and subjected to isomerization under alkaline conditions. By performing, the compound (1
91) is obtained. The compound (192) is obtained by the Wittig reaction between the compound (191) and the compound (59). Compound (192) was converted to Pd
Compound (193) is obtained by hydrogenation under a catalyst, and then oxidized with PCC to obtain compound (194).
After reducing compound (191) with sodium borohydride to compound (195), compound (196) is obtained by bromination with carbon tetrabromide, and further by cyanation with sodium cyanide Compound (197) is obtained. Compound (197) is hydrolyzed under alkaline conditions to give carboxylic acid
The compound (198) is then heated in methanol under acidic conditions to give the compound (199). Compound
Compound (200) is obtained by reducing (199) with isobutylaluminum hydride (DIBAH). Also, compounds
Compound (200) can also be obtained by reducing (199) with lithium borohydride to obtain compound (214) and then oxidizing it with PCC.

Compound (11) and compounds (189), (194) and (20)
0), (191), and the compounds (201), (202), (203), (204) by Wittig reaction with (180) and (185), respectively.
And (205) are obtained. These compounds are hydrogenated under a Pd catalyst to obtain a compound (206), and then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (207). Compound (207) is also
It can also be obtained by dehydration condensation of compound (206) with acrylic acid or methacrylic acid by DCC, and Mitsunobu reaction.

When l = m = 1: Compounds (181) and (18)
Compound (208) is obtained by an etherification reaction of 6) with compound (36) under alkaline conditions. The compound (208) is converted into a compound (209) by a hydrogenation reaction, and then brominated with carbon tetrabromide or the like to obtain a compound (210).

The compound (211) is obtained by the Wittig reaction between the compound (191) and the compound (17), and further the compound (212) is obtained by reacting hydrogen gas under a Pd catalyst.
Compound (213) is obtained by brominating compound (212) with carbon tetrabromide or the like.

Compound (199) was reduced to compound (214).
Similarly, bromination gives compound (215).

Compound (216) is obtained by a condensation reaction of each of compounds (210), (213), (215) and (196) with compound (1) under alkaline conditions. After reducing the compound (216) with lithium borohydride to give a compound (217), the compound (218) is obtained by reacting acrylic acid chloride or methacrylic acid chloride. Compound (21
8) can also be obtained by dehydration-condensation of compound (217) with acrylic acid or methacrylic acid by DCC or Mitsunobu reaction.

(Synthetic route 11) In the above formula (I),
Y is -COO-, R ^A and R ^B is described the case of formula (II). FIG. 15 schematically shows the synthesis route 11.

When 1, m ≠ 1: Compound (148) and Compound
Compound (219) is obtained by an etherification reaction with (36),
Furthermore, the compound (220) is obtained by performing debenzylation with hydrogen gas in the presence of a Pd catalyst.

After deriving each of the compounds (96), (88) and (93) into an acid chloride, the compounds (148), (169) and (16)
By performing an esterification reaction with each of 6) and (220), compound (221) is obtained. Also, compound (96),
Compounds (148), (169), (1) with each of (88) and (93)
Compound (221) can also be obtained by condensation with each of 66) and (220) using dicyclohexylcarbodiimide (DCC) or the Mitsunobu reaction. The compound (221) is debenzylated with hydrogen gas to obtain a compound (222), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (223). Compound (223) can also be obtained by reacting compound (222) with acrylic acid or methacrylic acid.
It can also be obtained by dehydration condensation by CC and Mitsunobu reaction.

(Synthetic Route 12) In the above formula (I),
Y is -COO-, R ^A is represented by formula (III), and R ^{B is}
Is represented by the formula (II) or (III). FIG. 16 schematically shows the synthesis route 12.

L, when m ≠ 1: Compounds (96), (88) and (93) are each converted to an acid chloride, and then
By performing an esterification reaction with each of (181), (186), (195), (214), (209) and (212), compound (224)
Is obtained. Further, dicyclohexylcarbodiimide (DCC) of each of compounds (96), (88) and (93) and each of compounds (181), (186), (195), (214), (209) and (212) )) Or the Mitsunobu reaction to give compound (224). The compound (224) is debenzylated with hydrogen gas to obtain a compound (225), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (226). Compound (226) is also
It can also be obtained by the dehydration condensation of compound (225) with acrylic acid or methacrylic acid by DCC or Mitsunobu reaction.

(Synthetic route 13) In the above formula (I),
Y is -OCO-, R ^A and R ^B is described the case of formula (II). FIG. 17 schematically shows the synthesis route 13.

L, m ≠ 1: Compound (227) is obtained by alkaline hydrolysis of Compound (168).

The compound (228) is obtained by an etherification reaction of the compound (115) with the compound (148). Compound (228)
By removing the benzyl group by hydrogenation, the compound
(229) is obtained, and further oxidized with PCC to obtain a compound (230). Compound (231) is obtained by oxidizing compound (230) with potassium permanganate or the like.

Compound (232) is obtained by a coupling reaction between compound (115) and compound (153), and further, the protecting group is removed by hydrogenation to obtain compound (233). The compound (233) is oxidized with PCC to obtain a compound (234), and then oxidized with potassium permanganate or the like to obtain a compound (235).

After deriving each of the compounds (227), (231) and (235) into an acid chloride, the compounds (106), (108),
Compound (236) is obtained by performing an esterification reaction with each of (9), (109) and (112). Further, each of the compounds (227), (231) and (235) and the compound (10
Compound (236) can also be obtained by condensation with each of 6), (108), (9), (109) and (112) using dicyclohexylcarbodiimide (DCC) or Mitsunobu reaction. The compound (236) is debenzylated with hydrogen gas to obtain a compound (237), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (238). Compound (238) can also be obtained by dehydration-condensation of compound (237) with acrylic acid or methacrylic acid by DCC, and Mitsunobu reaction.

(Synthetic route 14) In the above formula (I),
Y is -OCO-, R ^A is represented by formula (III), and R ^{B is}
Is represented by the formula (II) or (III). FIG. 18 schematically shows the synthesis route 14.

L, m ≠ 1: Compound (239) is oxidized with potassium permanganate or the like to give Compound (239)
Is obtained.

The compound (240) is obtained by a Wittig reaction of the compound (191) with the compound (36), and further, the compound (241) is obtained by hydrogenation under a Pd catalyst. Compound (24
Compound (242) is obtained by oxidizing 1) with PCC, and further compound (243) is obtained by oxidizing it with potassium permanganate or the like.

Compound (244) is obtained by etherification of each of compounds (181) and (186) with compound (115) under alkaline conditions, and further compound (245) is obtained by debenzylation by hydrogenation. can get. Compound (246) is obtained by PCC oxidation of compound (245), and further compound (2) is obtained by oxidation with potassium permanganate.
47) is obtained.

After deriving each of the compounds (239), (243), (247) and (198) into an acid chloride, the compounds (106),
Compound (248) is obtained by carrying out an esterification reaction with each of (108), (9), (109) and (112). In addition, each of compounds (239), (243), (247) and (198) and compounds (106), (108), (9), (109) and (112) of dicyclohexylcarbodiimide (DCC )) Or the Mitsunobu reaction to give compound (248). The compound (248) is debenzylated with hydrogen gas to obtain a compound (249), which is then reacted with acrylic acid chloride or methacrylic acid chloride to obtain a compound (250). Compound (250) is also compound (249)
And acrylic acid or methacrylic acid with DCC for dehydration condensation and Mitsunobu reaction.

(Synthetic route 15) In the above formula (I),
Y is -O-, R ^A and R ^B is described the case of formula (II). FIG. 19 schematically shows the synthesis route 15.

When l, m ≠ 1: Compounds (106), (108),
(9), (109) and (112), and compounds (170) and (1
By etherification reaction with each of (67) and (164),
Alternatively, compound (251) is obtained by an etherification reaction of each of compounds (10), (139) and (140) with each of compounds (148), (169), (166) and (220). .
Compound (251) is compound (10), (139) and (140)
Instead of compounds (106), (108), (9), (109) and (1
It can also be obtained by performing an etherification reaction using a tosylate obtained by allowing p-toluenesulfonic acid chloride to act on 12). The compound (251) is hydrogenated under a Pd catalyst to give the compound (252). The compound (253) is obtained by further reacting acrylic acid chloride or methacrylic acid chloride. Compound (25
3) can also be obtained by dehydration-condensation of compound (252) with acrylic acid or methacrylic acid by DCC or Mitsunobu reaction.

(Synthesis Route 16) In the above formula (I),
Y is -O-, R ^A is represented by Formula (III), and the R ^B describes a case of the formula (II) or (III). FIG.
0 schematically illustrates the synthesis route 16.

When 1, m ≠ 1: Compounds (106), (108),
(9), (109) and (112), and compounds (196) and (2
15), by etherification reaction with each of (210) and (213), or with each of compounds (10), (139) and (140), and compounds (181), (186), (195), (214), (212)
Compound (254) is obtained by etherification reaction with each of (209) and (209). Compound (254) is compound (1)
Instead of (0), (139) and (140), compounds (106), (10
8), (9), (109) and (112) can also be obtained by performing an etherification reaction using a tosylate obtained by reacting p-toluenesulfonic acid chloride. Compound (25
4) is hydrogenated under Pd catalyst to give compound (255)
Is obtained, and further, by reacting acrylic acid chloride or methacrylic acid chloride, a compound (256)
Is obtained. Compound (256) can also be obtained by dehydration-condensation of compound (255) with acrylic acid or methacrylic acid by DCC or Mitsunobu reaction.

(Liquid crystal display element) The liquid crystal display element of the present invention comprises:
A liquid crystal layer having a pair of substrates at least one of which is transparent, a polymer or polymer wall sandwiched between the substrates, and a liquid crystal region surrounded by the polymer or polymer wall; Alternatively, the polymer wall is formed from a monomer containing at least one polymerizable compound of the present invention as a polymerization precursor.

The liquid crystal material used in the present invention is not particularly limited as long as it is an organic mixture showing a liquid crystal state at about normal temperature. Nematic liquid crystal (dual-frequency driving liquid crystal, liquid crystal with Δε <0) is preferable as the liquid crystal material. ), A cholesteric liquid crystal (particularly, a liquid crystal having a selective reflection characteristic with respect to visible light), a smectic liquid crystal, a discotic liquid crystal, and the like. Among these, a nematic liquid crystal or a cholesteric liquid crystal, or a nematic liquid crystal to which a chiral agent is added is particularly preferable in terms of characteristics.
In a nematic liquid crystal to which a chiral agent is added,
It is preferable to add a chiral agent so as to have a helical pitch of 10 μm or more due to problems such as hysteresis, uniformity, and coloring due to d △ n (phase difference). Further, a liquid crystal excellent in chemical reaction resistance is preferred because a photopolymerization reaction is involved during processing. Such a liquid crystal is a liquid crystal having a functional group such as a fluorine atom in the compound, specifically, ZLI-4801-000,
Examples include ZLI-4801-001, ZLI-4792, and MLC-6419 (manufactured by Merck). These liquid crystal materials can be used alone or as a mixture.

The mixing ratio of the liquid crystal material to the monomer containing at least the polymerizable compound of the present invention is such that the weight ratio of the liquid crystal material to the monomer (liquid crystal material: polymerizable compound) is 60:40 to 98: 2 is preferred. When the amount of the monomer is more than 60:40, the liquid crystal region that changes with respect to the voltage applied to the electrode in the liquid crystal element is reduced, so that the contrast is often insufficient.
On the other hand, when the monomer content is less than 98: 2, the polymer wall cannot be formed sufficiently, and the strength of the liquid crystal display element (for example,
Pressure resistance and impact resistance) are insufficient and there are many practical problems.

The liquid crystal display device of the present invention can be manufactured, for example, by the following procedure: First, a liquid crystal cell using ITO (indium oxide / tin oxide composite, film thickness: 50 nm) as a transparent electrode is manufactured. A predetermined photomask is arranged at the position. A homogeneous mixture of a monomer containing at least the polymerizable compound of the present invention and a liquid crystal material is injected into the cell by capillary, to produce a liquid crystal cell. Then, a liquid crystal cell having a polymer (wall) surrounding the liquid crystal region by irradiating ultraviolet rays with a high-pressure mercury lamp capable of obtaining a parallel light beam from the photomask side while applying a voltage between the transparent electrodes to cure the monomer. Is prepared. Polarizing plates are arranged on both sides of the substrate of the liquid crystal cell so that their optical axes have a predetermined angle, thereby producing a liquid crystal display element.

The liquid crystal device obtained by using the polymerizable compound of the present invention has the following advantages. (1) Since the liquid crystal molecules are almost upright with respect to the substrate (when Δε> 0) when a saturation voltage is applied, the polarizing plate Have viewing angle characteristics, and (2) the liquid crystal layer has a retardation
There may be a region where the viewing angle characteristics are not sufficient in the ° direction.
As a cause of (2), the light incident from the axial direction has only a component of only ordinary light or extraordinary light when crossing the refractive index ellipsoid of the liquid crystal layer, but it has a 45 ° direction from the polarization axis of the polarizing plate. When light enters from, because it has both components of ordinary light and extraordinary light when crossing the refractive index ellipsoid of the liquid crystal layer (apparently,
This is because the polarization axes of the polarizing plates that are orthogonal to each other correspond to the state in which they are open to each other), which results in elliptically polarized light and significant light leakage. Therefore, it is preferable that the retardation of the liquid crystal layer is made as small as possible, and elliptically polarized light is hardly generated. However, the transmittance T ₀ when no voltage is applied is affected by the retardation of the liquid crystal layer.
A thickness of 300 nm to 650 nm is preferable from the viewpoint of ensuring omnidirectional viewing angle characteristics and cell brightness. (Below 300 nm, the brightness at the time of turning off the voltage cannot be ensured, resulting in a dark display.) The twist angle is preferably 45 to 150 °, and the brightest is preferably around 90 °, which satisfies the first minimum condition.

When a liquid crystal display device is produced using the polymerizable compound of the present invention, the orientation of the liquid crystal molecules is improved, but the orientation of the liquid crystal molecules can be controlled by using various orientation methods. As an alignment method that can be used in the present invention, a rubbing method in which a polymer material such as polyimide or an inorganic material is applied to a substrate used for manufacturing a liquid crystal cell and then rubbed with a cloth;
Vertical alignment method for applying a compound having low surface tension; SiO ₂
And the like, a method using a horizontal alignment film without rubbing treatment, a method using an untreated substrate (a substrate having a transparent electrode provided on the substrate), and the like.

As the substrate that can be used in the liquid crystal display device of the present invention, any of a transparent substrate and a non-transparent substrate can be used. Examples of the transparent substrate include a glass substrate and a plastic substrate such as a polymer film. Examples of the non-transparent substrate include a substrate on which a metal thin film is formed, a Si substrate, and the like. When used as a reflective liquid crystal display device, a substrate on which a metal thin film is formed is effective. Also,
The plastic substrate is preferably formed of a material that does not have a visible light absorption region. For example, PET,
Acrylic polymers, polycarbonates and the like can be mentioned. When a plastic substrate is used, the substrate itself may be provided with a polarizing ability. Furthermore, it is also possible to use a laminated substrate obtained by combining two kinds of these different types of substrates, and it is also possible to use a laminated substrate obtained by combining two substrates of the same type but different in thickness.

When a conventional liquid crystal alignment technique such as rubbing or oblique vapor deposition of SiO ₂ is applied to the liquid crystal cell formed by the above forming method, high contrast can be obtained by sandwiching the liquid crystal cell between two polarizing plates. With low driving voltage,
A liquid crystal display device in which a liquid crystal of a conventional alignment control type liquid crystal display mode (TN, STN, ECB, ferroelectric liquid crystal) having a sharp voltage-transmittance characteristic is quasi-solidified in a polymer can be manufactured.

The liquid crystal molecules in the liquid crystal region of the liquid crystal display device thus manufactured can take any alignment state. Representative examples of the orientation state include axial symmetry, radial or concentric orientation, spiral orientation, and random orientation.

The liquid crystal display device of the present invention is not particularly limited, but may be a simple matrix drive, a-Si TFT, p-S
It can be driven by an active driving method using an active element such as an iTFT or MIM.

The operation will be described below.

When a liquid crystal display element of a display mode in which the alignment regulating force is controlled on a substrate is manufactured from a mixture of a liquid crystal material and a polymerizable resin material such as a photocurable resin, usually, a liquid crystal element is provided between the alignment film and the liquid crystal region. A polymer layer in which a polymer and a liquid crystal are mixed is formed. This polymer layer generally tends to weaken the alignment regulating force of the alignment film on the liquid crystal molecules. On the contrary,
When the polymer layer contains a polymer formed from a monomer containing the polymerizable compound of the present invention, a portion derived from the polymerizable compound of the present invention in the polymer has a skeleton similar to a liquid crystal material. Therefore, the ability to exert an alignment control effect on liquid crystal molecules in the liquid crystal region appears in the polymer layer. As a result, the alignment state of the liquid crystal is stabilized.

In a liquid crystal display device in which the liquid crystal molecules in the liquid crystal region are oriented symmetrically with respect to the axis (the axis perpendicular to the substrate surface), in most cases, a reverse tilt (see FIG. 29)). However, by using the polymerizable compound of the present invention, the occurrence of disclination lines at the time of applying a voltage, which has deteriorated the black display level, is suppressed. Moreover, since the polymerizable compound of the present invention is a polyfunctional compound having a liquid crystal-like skeleton and having a branched polymerizable active group, it easily forms a three-dimensional network structure and has excellent reactivity. . Therefore, the polyfunctional compound of the present invention maintains the properties of the conventional monofunctional “polymerizable compound having a liquid crystal-like skeleton”, and at the same time, reduces the deterioration of the characteristics of the liquid crystal display device due to the unreacted compound. However, the characteristics of the polyfunctional compound such as improvement of the glass transition temperature (Tg) of the polymer can be realized at the same time. Therefore, the polymerizable compound of the present invention is extremely effective from the viewpoint of display characteristics and strength (for example, pressure resistance and heat resistance) of a liquid crystal display device. In addition, the polymerizable compound of the present invention is also effective against problems such as deterioration of response speed due to addition of the polymerizable compound, deterioration of threshold characteristics or steepness of voltage-transmittance characteristics, which have conventionally been problems. It can be a solution. As mentioned above,
By using the polymerizable compound of the present invention, the display characteristics (for example, viewing angle characteristics, contrast, response speed, threshold characteristics, sharpness), strength (for example, pressure resistance, impact resistance) and heat resistance of the liquid crystal display element are obtained. Sex can be dramatically improved.

The present inventors have studied the polymerizable compounds as described above, and by combining these polymerizable compounds with a liquid crystal material, a liquid crystal droplet surrounded by a polymer has been obtained.
The size of the (liquid crystal area) was made almost the same as the pixel, and we examined a method in which almost one liquid crystal droplet was regularly arranged for one pixel. As a result, the following two methods were extremely effective. Was found.

Irradiation with UV light having UV illuminance irregularity which is regular at the time of processing and which is close to the size of a liquid crystal droplet substantially equal to the size of a pixel is performed so that a region corresponding to a large part of the pixel is shielded from the UV light. A method of manufacturing a liquid crystal display device having a liquid crystal layer having a liquid crystal region surrounded by a polymer wall, and a method in which materials having different interface free energies for a liquid crystal phase and an isotropic phase are previously patterned on a substrate. Formed,
A method of fabricating a liquid crystal display device having a liquid crystal region surrounded by polymer walls by patterning and controlling free energy such as arranging a liquid crystal phase based on the surface pattern.

[0141]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. The abbreviations described in the examples mean the following.

GC: Gas chromatography HPLC: High performance liquid chromatography TLC: Thin layer chromatography IR: Infrared absorption spectrum Mass: Mass spectrum bp: Boiling point mp: Melting point Y: Yield (Example 1) A polymerizable compound was synthesized.

[0143]

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The synthesis procedure will be described below.

(A) Synthesis of a compound represented by the following formula:

[0146]

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In a 1 liter flask, 34.6 g of 4-bromophenol, 37.9 g of 2,3-difluorophenylboronic acid, 380 ml of dimethoxyethane, 380 ml of water, 97.8 g of cesium carbonate, and 7 g of tetrakistriphenylphosphine palladium
And stirred under reflux for 20 hours. The reaction solution was poured into water, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 9/1) and recrystallized from hexane to give 2,3-difluoro-4'-hydroxybiphenyl (30.9).
g (Y: 75%) was obtained. The purity of the obtained compound was 99.8 by GC.
% And mp was 132-134.4 ° C.

(B) Synthesis of the compound represented by the following formula:

[0149]

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In a 200 ml flask, 5.0 g of 2,3-difluoro-4'-hydroxybiphenyl, 11-bromo-1-undecanol
7.3 g, potassium carbonate 6.7 g, and methyl ethyl ketone 15
0 ml was charged and the mixture was stirred under reflux for 20 hours. The reaction solution was poured into water, and the organic layer was extracted with toluene. After the toluene layer was washed with water and dried over sodium sulfate, the solvent was distilled off, and the residue was recrystallized from acetone to give 2,3-difluoro-4 '-(11-hydroxyundecyl) oxybiphenyl 8 g (Y: 88%).
The purity of the obtained compound was 98.8% by GC.

(C) Synthesis of a compound represented by the following formula:

[0152]

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In a 200 ml flask, 2,3-difluoro-4 '-(11
8 g of -hydroxyundecyl) oxybiphenyl and 100 ml of carbon tetrachloride were charged. A solution of 2.3 g of phosphorus tribromide dissolved in 50 ml of carbon tetrachloride was added dropwise to the reaction system under cooling with ice water, and the mixture was stirred at room temperature for 3 hours and at reflux for 2 hours. The reaction solution was poured into water, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off.
The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/9), and further recrystallized from hexane to give 2,3-difluoro-4 ′-(11-bromoundecyl) oxybiphenyl 4.5. g (Y: 47.8%) was obtained. The purity of the obtained compound was 95.3% by GC.

(D) Synthesis of a compound represented by the following formula:

[0155]

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A 100 ml flask whose inside was replaced with argon was charged with 0.62 g of sodium ethoxide and 1.5 ml of diethyl malonate.
g, and 50 ml of absolute ethanol were charged. 20 ml of a tetrahydrofuran solution in which 4 g of 2,3-difluoro-4 '-(11-bromoundecyl) oxybiphenyl was dissolved was added to this reaction system.
Was added dropwise, and the mixture was stirred under reflux for 8 hours. The reaction solution was poured into diluted hydrochloric acid, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene), and 4 g of 2,3-difluoro-4 '-[12,12-bis (ethoxycarbonyl) dodecyl] oxybiphenyl (Y:
84.7%). The purity of the obtained compound was 99.8% by GC.

(E) Synthesis of a compound represented by the following formula:

[0158]

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In a 100 ml flask, add lithium borohydride
1.7 g and 20 ml of tetrahydrofuran were charged. To this reaction system, 60 ml of a tetrahydrofuran solution in which 4 g of 2,3-difluoro-4 '-[12,12-bis (ethoxycarbonyl) dodecyl] oxybiphenyl was dissolved was added dropwise, and the mixture was stirred under reflux for 18 hours. Cold diluted hydrochloric acid was added to the reaction solution, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue is subjected to silica gel column chromatography (eluent: ethyl acetate / toluene = 8/2).
And recrystallized from acetone to give 2,3-difluoro
2.4 g of -4 '-[12,12-bis (hydroxymethyl) dodecyl] oxybiphenyl (Y: 71.6%) was obtained. The purity of the obtained compound was 99.6% by HPLC.

(F) Synthesis of a compound represented by the following formula:

[0161]

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In a 200 ml flask, 2,3-difluoro-4 '-[1
2,12-bis (hydroxymethyl) dodecyl] oxybiphenyl 2.4 g, triethylamine 1.3 g, and tetrahydrofuran 100 ml were charged. To this reaction system was added dropwise a solution of acrylic acid chloride (1.1 g) in tetrahydrofuran (15 ml) under ice-water cooling, and the mixture was returned to room temperature and stirred for 3 hours. The reaction solution was poured into water, and the organic layer was extracted with ether. The ether layer was washed with dilute hydrochloric acid and then with water, dried over sodium sulfate and evaporated. The residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 20/1), and further recrystallized from hexane to give 2,3-difluoro-4 '-[12,12-bis (acryloyl). 1.7 g (Y: 57%) of [oxymethyl) dodecyl] oxybiphenyl were obtained. The purity of the obtained compound was 99.6% by GC, 100% by HPLC, and TLC
And the mp of the obtained compound is 33.4 ° C. to 3
4.4 ° C.

According to the result of IR measurement and the fact that a molecular ion peak was observed at 542 in Mass analysis,
Also, from the relationship between the raw materials used, it was confirmed that the obtained substance was a compound represented by the above formula (5).

Example 2 A polymerizable compound represented by the following formula 12 was synthesized.

[0165]

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The synthesis procedure will be described below.

(A) Synthesis of a compound represented by the following formula:

[0168]

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In a 300 ml flask, 60% sodium hydride
2.4 g and 100 ml of anhydrous tetrahydrofuran were charged. To this reaction system, a solution of 11.3 g of benzyl bromide in 15 ml of tetrahydrofuran, and 6-bromohexanol
15 ml of a tetrahydrofuran solution in which 10.9 g was dissolved and 0.1 g of tetrabutylammonium iodide were added, and the mixture was stirred under reflux for 3 hours. The reaction solution was poured into water, and the organic layer was extracted with toluene. After the toluene layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1 /
Purification according to 3) and distillation under reduced pressure were performed to obtain 8.6 g of 1-bromo-6-benzyloxyhexane (Y: 52.8%). The purity of the obtained compound was 97.9% by GC, and bp was 115 to 127 ° C / 0.4.
mmHg.

(B) Synthesis of a compound represented by the following formula:

[0171]

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In a 200 ml flask, add sodium ethoxide
2.7 g and 100 ml of absolute ethanol were charged. To this reaction system, 20 ml of an ethanol solution of 7 g of diethyl malonate was added.
The mixture was added dropwise at 0 ° C and stirred for 2 hours. Next, 20 ml of an ethanol solution of 9 g of 1-bromo-6-benzyloxyhexane was added dropwise, the mixture was stirred under reflux for 3 hours, and the reaction solution was poured into diluted hydrochloric acid. Extract the organic layer with ether, wash the ether layer with water,
After drying with sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 9/1) to obtain 11.5 g of diethyl 2- (6-benzyloxyhexyl) malonate (Y: 98%). The purity of the obtained compound was 86.3% by GC.

(C) Synthesis of a compound represented by the following formula:

[0174]

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In a 200 ml flask, 60% sodium hydride
1.5 g and 30 ml of anhydrous dimethylformamide were charged. To this reaction system, 30 ml of a dimethylformamide solution of 11.5 g of diethyl 2- (6-benzyloxyhexyl) malonate was added dropwise under cooling with ice water, followed by stirring at room temperature for 1 hour and at 130 ° C. for 30 minutes. Next, 10 g of 1-bromo-6-benzyloxyhexane
Was added dropwise, and the mixture was stirred for 3 hours, and then the reaction solution was poured into diluted hydrochloric acid. The organic layer was extracted with ether, and the ether layer was washed with water and dried over sodium sulfate,
The solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 9/1) to give 14.8 g of diethyl 2,2-bis (6-benzyloxyhexyl) malonate (Y: 91.5%). The purity of the obtained compound was 94.7% by GC.

(D) Synthesis of the compound represented by the following formula:

[0177]

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In a 100 ml flask, diethyl 2,2-bis (6-
14.8 g of benzyloxyhexyl) malonate, 0.5 g of water, 2.3 g of lithium chloride, and 50 ml of dimethyl sulfoxide were charged and stirred at 180 ° C. for 12 hours. Pour the reaction into water,
The organic layer was extracted with methylene chloride. After the methylene chloride layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 9/1), and 9.4 g of ethyl 2,2-bis (6-benzyloxyhexyl) acetate (Y: 72.
9%). The purity of the obtained compound was 97.9% by GC.

(E) Synthesis of a compound represented by the following formula:

[0180]

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In a 500 ml flask, 12 g of ethyl 2,2-bis (6-benzyloxyhexyl) acetate, 250 m of methanol
l, and 100 ml of an aqueous solution of 16.8 g of 85% potassium hydroxide were charged and stirred under reflux for 2 hours. The reaction solution was poured into diluted hydrochloric acid, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue was recrystallized from a mixed solvent of hexane / acetone to give 2,2-bis (6
6.2 g of (benzyloxyhexyl) acetic acid (Y: 55%) were obtained.

(F) Synthesis of a compound represented by the following formula:

[0183]

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In a 100 ml flask, 6 g of 6-bromo-1-hexanol, 5.7 g of 2,3-difluoro-4′-hydroxybiphenyl,
7.6 g of potassium carbonate and 70 ml of methyl ethyl ketone were charged, and the mixture was stirred under reflux for 20 hours. Pour the reaction into water,
The organic layer was extracted with toluene. After the toluene layer was washed with water and dried over sodium sulfate, the solvent was distilled off, and the residue was recrystallized from acetone to give 5.4 g of 2,3-difluoro-4 ′-(6-hydroxyhexyl) oxybiphenyl (Y: 63.5%). The purity of the obtained compound was 99.9% by GC.

(G) Synthesis of a compound represented by the following formula:

[0186]

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In a 100 ml flask, 2.47 g of 2,2-bis (6-benzyloxyhexyl) acetic acid, 1.85 g of 2,3-difluoro-4 ′-[6-hydroxyhexyl] oxybiphenyl, 1.6 g of triphenylphosphine, 50 ml of tetrahydrofuran was charged. 1.1 g of diethyl azodicarboxylate was added dropwise to this reaction system at 5 ° C., and the mixture was returned to room temperature and stirred for 8 hours. The reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4) to give 6- [2,3-difluorobiphenyl-4′-yl] oxyhexyl 2, 4 g (Y: 97.8%) of 2-bis (6-benzyloxyhexyl) acetate was obtained. The purity of the obtained compound is HPL
C was 99%.

(H) Synthesis of a compound represented by the following formula:

[0189]

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In a 300 ml autoclave, 6 g of 6- [2,3-difluorobiphenyl-4'-yl] oxyhexyl 2,2-bis (6-benzyloxyhexyl) acetate, 10% Pd-C 1.3
g, and 150 ml of tetrahydrofuran.
It was set at 10 kg / cm ² and stirred at room temperature for 2 days. After the catalyst was removed by filtration and the filtrate was concentrated, the residue was subjected to silica gel column chromatography (eluent: toluene / ethyl acetate = 2/2).
Purification according to 3) gave 2.6 g of 6- [2,3-difluorobiphenyl-4'-yl] oxyhexyl 2,2-bis (6-hydroxyhexyl) acetate (Y: 90%). The purity of the obtained compound was 99.3% by HPLC.

(I) Synthesis of a compound represented by the following formula:

[0192]

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In a 200 ml flask, 2.6 g of 6- [2,3-difluorobiphenyl-4'-yl] oxyhexyl 2,2-bis (6-hydroxyhexyl) acetate, 1.2 g of triethylamine,
And 100 ml of tetrahydrofuran, 1.1 g of acrylic acid chloride dissolved in a small amount of tetrahydrofuran was added dropwise thereto under cooling with ice water, and the mixture was returned to room temperature and stirred for 3 hours. The reaction solution was poured into water, and the organic layer was extracted with ether. The ether layer was washed with dilute hydrochloric acid and then with water, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / toluene = 1/9) to give 6- [2,3-difluorobiphenyl-4'-
[Il] oxyhexyl 2,2-bis (6-acryloyloxyhexyl) acetate (0.9 g, Y: 28%) was obtained. The obtained compound was liquid at room temperature. The purity of the obtained compound was 99% by HPLC and 1 spot by TLC.

According to the results of IR measurement and the fact that a molecular ion peak was observed at 656 in Mass analysis,
In addition, from the relationship between the raw materials used, it was confirmed that the obtained substance was a compound represented by the above formula (12).

Example 3 A polymerizable compound represented by the following formula 22 was synthesized.

[0196]

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The following shows the synthesis procedure.

(A) Synthesis of a compound represented by the following formula:

[0199]

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In a 100 ml flask, 3.0 g of 2,2-bis (6-benzyloxyhexyl) acetic acid, 2.8 g of 2,3-difluoro-4 ′-[11-hydroxyundecyl] oxybiphenyl, 2.2 g of triphenylphosphine, And 50 ml of tetrahydrofuran, and 1.4 g of diethyl azodicarboxylate was added dropwise at 5 ° C., and the mixture was returned to room temperature and stirred for 8 hours. The reaction solution is concentrated, and the residue is subjected to silica gel column chromatography (eluent:
Purification by ethyl acetate / hexane = 1/9) gave 11- [2,3
-Difluorobiphenyl-4'-yl] oxyundecyl 2,2
-Bis (6-benzyloxyhexyl) acetate 5 g (Y: 9
2.6%). The purity of the obtained compound was 98% by HPLC.

(B) Synthesis of a compound represented by the following formula:

[0202]

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In a 300 ml autoclave, 11- [2,3-difluorobiphenyl-4'-yl] oxyundecyl 2,2-bis (6
-Benzyloxyhexyl) acetate 4.9g, 10% Pd-C
1.5 g and 100 ml of tetrahydrofuran were charged, and the mixture was stirred at room temperature for 2 days at a hydrogen pressure of 10 kg / cm ² . After the catalyst was filtered off and the filtrate was concentrated, the residue was subjected to silica gel column chromatography (eluent: toluene / ethyl acetate =
7/3) to give 11- [2,3-difluorobiphenyl-
[4′-yl] oxyundecyl 2,2-bis (6-hydroxyhexyl) acetate (3.7 g, Y: 97.5%) was obtained. The purity of the obtained compound was 98% by HPLC.

(C) Synthesis of a compound represented by the following formula:

[0205]

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In a 100 ml flask, 3.66 g of 11- [2,3-difluorobiphenyl-4′-yl] oxyundecyl 2,2-bis (6-hydroxyhexyl) acetate, 1.36 g of triethylamine
g, and 30 ml of benzene. Under ice-water cooling, 1.2 g of acrylic acid chloride was dissolved in a small amount of benzene and added dropwise to the reaction system, and the mixture was returned to room temperature and stirred for 3 hours. The reaction solution was poured into water, and the organic layer was extracted with ether. The ether layer was washed with dilute hydrochloric acid and then with water, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / toluene = 1/20) to give 11-. [2,3-difluorobiphenyl-4'-yl] oxyundecyl 2,2-bis (6-acryloyloxyhexyl)
1.36 g of acetate (Y: 32%) was obtained. The obtained compound was liquid at room temperature. The purity of the obtained compound was determined by HPLC.
99%, 1 spot by TLC.

According to the results of IR measurement and the fact that a molecular ion peak was observed at 726 in Mass analysis,
In addition, from the relationship between the raw materials used, it was confirmed that the obtained substance was a compound represented by Chemical Formula 22 above.

Example 4 A polymerizable compound represented by the following formula 26 was synthesized.

[0209]

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The synthesis procedure is shown below.

(A) Synthesis of a compound represented by the following formula:

[0212]

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In a 1 liter flask, 10 g of 1,16-hexadecanediol, 26 g of 48% hydrobromic acid, and 40
0 ml, and remove the water in the system at reflux temperature.
Stirred for hours. After washing the reaction solution with water and drying over sodium sulfate,
The solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 9/1) and recrystallized from hexane to give 5.7 g of 16-bromo-1-hexadodecanol (Y: 46%). Obtained. The purity of the obtained compound was 95% by GC.

(B) Synthesis of a compound represented by the following formula:

[0215]

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A 100 ml flask was charged with 3 g of 16-bromo-1-hexadodecanol, 1.9 g of 2,3-difluoro-4'-hydroxybiphenyl, 2.6 g of potassium carbonate and 50 ml of methyl ethyl ketone, and stirred under reflux for 32 hours. did. The reaction solution was poured into water, and the organic layer was extracted with ether. The ether layer was washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue was recrystallized from acetone to give 3.5 g of 2,3-difluoro-4 '-(16-hydroxyhexadecyl) oxybiphenyl (Y: 84%). The purity of the obtained compound was 97.4% by GC.

(C) Synthesis of a compound represented by the following formula:

[0218]

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In a 100 ml flask, 3.4 g of 2,2-bis (6-benzyloxyhexyl) acetic acid, 3.3 g of 2,3-difluoro-4 ′-[16-hydroxyhexadecyl] oxybiphenyl, 2.3 g of triphenylphosphine, And 50 ml of tetrahydrofuran, 1.5 g of diethyl azodicarboxylate was added dropwise at 5 ° C., and the mixture was returned to room temperature and stirred for 8 hours. Concentrate the reaction,
The residue was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/9) to give 16-
[2,3-difluorobiphenyl-4'-yl] oxyhexadecyl 2,2-bis (6-benzyloxyhexyl) acetate 5.9
g (Y: 92.1%) was obtained. The purity of the obtained compound was determined by HPLC.
Was 98.3%.

(D) Synthesis of a compound represented by the following formula:

[0221]

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In a 300 ml autoclave, 16- [2,3-difluorobiphenyl-4'-yl] oxyhexadecyl 2,2-bis
(6-benzyloxyhexyl) acetate 5.8 g, 10% Pd-C
1.8 g and 100 ml of tetrahydrofuran were charged, and the mixture was stirred at room temperature for 2 days at a hydrogen pressure of 10 kg / cm ² . After the catalyst was filtered off and the filtrate was concentrated, the residue was subjected to silica gel column chromatography (eluent: toluene / ethyl acetate =
7/3) to give 16- [2,3-difluorobiphenyl-
4′-yl] oxyhexadecyl 2,2-bis (6-hydroxyhexyl) acetate (3.9 g, Y: 85.5%) was obtained. The purity of the obtained compound was 99.2% by HPLC, and mp was 45.2 to 48.8.
° C.

(E) Synthesis of a compound represented by the following formula:

[0224]

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In a 100 ml flask, 3.4 g of 16- [2,3-difluorobiphenyl-4'-yl] oxyhexadecyl 2,2-bis (6-hydroxyhexyl) acetate, 3 g of triphenylphosphine, 0.9 g of acrylic acid, And 30 ml of tetrahydrofuran. Under ice-cooling, 2 g of ethyl azodicarboxylate was dissolved in 10 ml of tetrahydrofuran and added dropwise to the reaction system, and the mixture was returned to room temperature and stirred for 3 hours. After concentrating the reaction mixture, the residue was purified by silica gel column chromatography.
(Eluent: ethyl acetate / toluene = 1/20), recrystallized from hexane to give 16- [2,3-difluorobiphenyl-
There was obtained 2.7 g (Y: 59.7%) of [4′-yl] oxyhexadecyl 2,2-bis (6-acryloyloxyhexyl) acetate.
The purity of the obtained compound was 99% by HPLC and one spot by TLC, and the mp was 33.8 to 35.5 ° C.

According to the result of IR measurement and the fact that a molecular ion peak was observed at 796 by Mass analysis,
In addition, from the relationship between the raw materials used, it was confirmed that the obtained substance was a compound represented by Chemical Formula 26 above.

Example 5 A polymerizable compound represented by the following formula was synthesized.

[0228]

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The following shows the synthesis procedure.

(A) Synthesis of a compound represented by the following formula:

[0231]

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In a 300 ml flask purged with argon, 60%
2.4 g sodium hydride and anhydrous tetrahydrofuran
100 ml was charged. In this reaction system, benzyl bromide 1
1.3 g of tetrahydrofuran solution 15 ml, 12-bromododecanol 15.9 g of tetrahydrofuran solution 15 ml, tetrabutylammonium iodide 0.1 g was added, and under reflux 2.5 g
Stirred for hours. The reaction solution was poured into water, and the organic layer was extracted with toluene. After the toluene layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/3) to give 1-bromo-12-benzyloxidedecane 14.0.
g (Y: 65.7%) was obtained. The purity of the obtained compound was 9 by GC.
8.4%.

(B) Synthesis of a compound represented by the following formula:

[0234]

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A 200 ml flask purged with argon was charged with 12.4 g of 1-bromo-12-benzyloxidedecane, 6.3 g of sodium iodide and 125 ml of acetone, and refluxed under reflux for 5 minutes.
Stirred for hours. After filtering off the insoluble matter and concentrating the filtrate, ether was added to the residue. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: toluene / hexane = 1/1) to give 1-iodo-12-benzyl oxide. 14.7 g (Y: 100%) of decane was obtained. The purity of the obtained compound was 96.1% by GC.

(C) Synthesis of a compound represented by the following formula:

[0237]

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In a 500 ml Schlenk tube purged with argon,
18.3 g of 1,2-difluorobenzene and 150 ml of anhydrous tetrahydrofuran were charged, 102 ml of a 1.6 M butyllithium-hexane solution was added dropwise at -60 to -70 ° C, and the mixture was stirred at the same temperature for 3 hours. To this, 80 ml of a tetrahydrofuran solution of 25.0 g of 1,4-cyclohexanedione / monoethylene ketal was added dropwise, the temperature was gradually raised to room temperature, and the mixture was stirred overnight.

After the reaction solution was acidified by adding 5% diluted hydrochloric acid, the organic layer was extracted with toluene. The toluene layer was washed with water, dried over sodium sulfate, and the solvent was distilled off. 1 g of p-toluenesulfonic acid monohydrate and 300 ml of toluene were added to the residue, and the mixture was heated and stirred for 9 hours while removing generated water. After the reaction solution was washed with water and dried over sodium sulfate, the solvent was distilled off to obtain 39.4 g of crude 4- (2,3-difluorophenyl) -3-cyclohexenone ethylene ketal (Y: 71.8%). . The purity of the obtained compound was 73.6% by GC.

(D) Synthesis of the compound represented by the following formula:

[0241]

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In a 500 ml autoclave, 4- (2,3-difluorophenyl) -3-cyclohexenone ethylene ketal 39.4
g, 150 ml of ethyl acetate and 1.0 g of 10% Pd-C were charged, and the mixture was stirred at room temperature for 43 hours at a hydrogen pressure of 10 kg / cm ² . After the catalyst was removed by filtration, the filtrate was concentrated, and 1,4-dioxane 225m
l, 675 ml of water and 1 g of p-toluenesulfonic acid monohydrate were added, and the mixture was stirred under reflux for 2 hours. The reaction solution was extracted with ether, the ether layer was washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene / hexane = 19: 1), and further distilled under reduced pressure to give 4- (2,3-difluorophenyl).
17.5 g (Y: 72%) of cyclohexanone was obtained. The purity of the obtained compound was 98.9% by GC, and the bp was 125 to 128 ° C / 0.6 m.
mHg.

(E) Synthesis of a compound represented by the following formula:

[0244]

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A 500 ml flask purged with argon was charged with (methoxymethyl) triphenylphosphonium chloride (27.4).
g, 9 g of potassium t-butoxide and 225 ml of anhydrous ether were added, and the mixture was stirred for 30 minutes under ice-water cooling. In this reaction system, 4- (2,3
50 ml of an ether solution of 16.8 g of-(difluorophenyl) cyclohexanone was added dropwise, and the mixture was stirred for 30 minutes under cooling with ice water and at room temperature for 8 hours. The precipitate was separated by filtration, the filtrate was washed with water, and dried over sodium sulfate. After the solvent was distilled off, the residue was subjected to silica gel column chromatography (eluent: toluene / hexane = 1).
/ 4) to give 1- (2,3-difluorophenyl) -4-
17.1 g of methoxymethylenecyclohexane (Y: 89.7%) was obtained. The purity of the obtained compound was 99.2% by GC.

(F) Synthesis of a compound represented by the following formula:

[0247]

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In a 200 ml flask, 17.1 g of 1- (2,3-difluorophenyl) -4-methoxymethylenecyclohexane, 3N
19 ml of hydrochloric acid and 80 ml of tetrahydrofuran are charged, and the mixture is refluxed.
Stir for 30 minutes. The reaction solution was poured into water, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off.

On the other hand, another flask was charged with 1 g of caustic potash and 170 ml of methanol. The above residue was dissolved in 85 ml of methanol and added dropwise to this reaction system at 0 to 3 ° C. After stirring at the same temperature for 1 hour, the reaction solution was poured into water, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off to obtain 14.3 g of trans-4- (2,3-difluorophenyl) cyclohexanecarbaldehyde (Y:
88.9%). The purity of the obtained compound was 95% by GC.

(G) Synthesis of the compound represented by the following formula:

[0251]

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In a 100 ml flask purged with argon, (b)
1-iodo-12-benzyloxidedecane obtained in 14.7
g, triphenylphosphine 9.2 g, and toluene 50 ml
And stirred under reflux for 30 hours. The solvent was distilled off under reduced pressure, the inside of the flask was replaced with argon again, and 70 ml of anhydrous tetrahydrofuran was added. In addition, under ice water cooling, 1.6
22.4 ml of a M butyllithium-hexane solution was added dropwise, and the mixture was returned to room temperature and stirred for 40 minutes.
35 ml of a tetrahydrofuran solution of 7.85 g of -4- (2,3-difluorophenyl) cyclohexanecarbaldehyde was added dropwise. After returning to room temperature and stirring all day and night, insolubles were filtered off,
The filtrate was diluted with methylene chloride. After the methylene chloride layer was washed with water and dried over sodium sulfate, the solvent was distilled off, and 11.9 g of 2,3-difluoro-1- [trans-4- {13-benzyloxy-1-tridecenyl} cyclohexyl] benzene (Y : 70.4%). The purity of the obtained compound was 96% by GC (E, Z mixture).

(H) Synthesis of a compound represented by the following formula:

[0254]

Embedded image

In a 500 ml autoclave, 2,3-difluoro-
1- [trans-4- {13-benzyloxy-1-tridecenyl}
Cyclohexyl] benzene (10.9 g), 10% Pd-C (1 g), ethanol (50 ml) and ethyl acetate (50 ml) were charged, and the hydrogen pressure was increased to 8%.
It was set to kg / cm ² and stirred at room temperature for 5 days. After the catalyst was filtered off and the filtrate was concentrated, the residue was subjected to silica gel column chromatography (eluent: toluene / ethyl acetate = 4/4).
Purification by 1) and recrystallization from acetone gave 5.7 g (Y: 64%) of 2,3-difluoro-1- [trans-4- (13-hydroxytridecyl) cyclohexyl] benzene. The purity of the obtained compound was 97.2% by GC and 99.8% by HPLC.

(I) Synthesis of a compound represented by the following formula:

[0257]

Embedded image

In a 100 ml flask, 2,3-difluoro-1- [trans-4- (13-hydroxytridecyl) cyclohexyl]
3 g of benzene, 3 g of 2,2-bis (6-benzyloxyhexyl) acetic acid, 2.2 g of triphenylphosphine, and 30 ml of tetrahydrofuran were charged. In this reaction system, under ice water cooling,
1.5 g of ethyl azodicarboxylate was added dropwise, and the temperature was returned to room temperature to give 2 g.
Stirred for hours. The reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 9/1) to give 13- [trans-4- (2,3-difluorophenyl) cyclohexyl] tridecyl 2, 2-screw
5.4 g of (6-benzyloxyhexyl) acetate (Y: 97%)
I got The purity of the obtained compound was 93.7% by HPLC.

(J) Synthesis of a compound represented by the following formula:

[0260]

Embedded image

In a 300 ml autoclave, 13- [trans-4-
(2,3-Difluorophenyl) cyclohexyl] tridecyl
5.3 g of 2,2-bis (6-benzyloxyhexyl) acetate,
1.7 g of 10% Pd-C and 100 ml of tetrahydrofuran were charged, and the mixture was stirred at room temperature for 2 days at a hydrogen pressure of 10 kg / cm ² . After the catalyst was filtered off and the filtrate was concentrated, the residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 7/3) to give 13- [trans-4- (2,3
-Difluorophenyl) cyclohexyl] tridecyl 2,2-
Bis (6-hydroxyhexyl) acetate 4.1 g (Y: 98
%). The purity of the obtained compound was 99% by HPLC.

(K) Synthesis of a compound represented by the following formula:

[0263]

Embedded image

In a 100 ml flask, 13- [trans-4- (2,3-
Difluorophenyl) cyclohexyl] tridecyl 2,2-
2.8 g of bis (6-hydroxyhexyl) acetate, 1 g of triethylamine and 30 ml of benzene were charged. Under cooling with ice water, 0.9 g of acrylic acid chloride was dissolved in a small amount of benzene and added dropwise to the reaction system, and the mixture was returned to room temperature and stirred for 3 hours. The reaction solution was poured into water, and the organic layer was extracted with ether. The ether layer was washed with dilute hydrochloric acid and then with water, dried over sodium sulfate and evaporated. The residue is subjected to silica gel column chromatography (eluent: ethyl acetate / toluene =
1/20) to give 13- [trans-4- (2,3-difluorophenyl) cyclohexyl] tridecyl 2,2-bis (6-acryloyloxyhexyl) acetate 1.12 g (Y: 33%). . The obtained compound was liquid at room temperature. The purity of the obtained compound was 99.6% by HPLC and one spot by TLC.

According to the result of IR measurement and the fact that a molecular ion peak was observed at 744 by Mass analysis,
In addition, from the relationship between the raw materials used, it was confirmed that the obtained substance was a compound represented by the above formula.

Example 6 A polymerizable compound represented by the following formula was synthesized.

[0267]

Embedded image

The synthesis procedure is described below.

(A) Synthesis of a compound represented by the following formula:

[0270]

Embedded image

A 300 ml flask was charged with 2.6 g of magnesium, a small amount of iodine and 70 ml of tetrahydrofuran. To this reaction system, 15.5 g of 1-bromo-12-benzyloxidedecane
60 ml of a tetrahydrofuran solution was added dropwise at 40 to 50 ° C. to prepare a Grignard reagent. After cooling to 5 ° C., a solution of 2.1 g of methyl formate in 20 ml of tetrahydrofuran was added dropwise, and the mixture was returned to room temperature and stirred for 2 hours and under reflux for 2 hours.

The reaction solution was poured into diluted hydrochloric acid, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene) and recrystallized from acetone to obtain 6.25 g of bis (12-benzyloxidedecyl) methanol (Y: 30.7%). The purity of the obtained compound was 94.7% by HPLC.

(B) Synthesis of a compound represented by the following formula:

[0274]

Embedded image

A 100 ml flask was charged with 3 g of bis (12-benzyloxidedecyl) methanol and 20 ml of pyridine.
To this reaction system, 1.15 g of p-toluenesulfonyl chloride
Was added and stirred at room temperature for 3 days. The reaction solution was diluted with ether, and the diluted solution was washed with diluted hydrochloric acid, an aqueous solution of sodium hydrogen carbonate and water in that order, and dried over sodium sulfate. After distilling off the solvent, the residue was recrystallized from acetone and bis (12-benzyloxidedecyl) methyl p-toluenesulfonate 1.6 g
(Y: 42%). The purity of the obtained compound was 9 by HPLC.
8.5%.

(C) Synthesis of a compound represented by the following formula:

[0277]

Embedded image

In a 100 ml flask, 60% sodium hydride
0.1 g and dimethylformamide 20 ml were charged. To this reaction system, 5 ml of a dimethylformamide solution of 0.42 g of 2,3-difluoro-4'-hydroxybiphenyl was added dropwise under cooling with ice water.
Stirred for a while. Next, 1.5 g of bis (12-benzyloxidedecyl) methyl p-toluenesulfonate was added, and the mixture was stirred under reflux for 12 hours. Then, the reaction solution was poured into water, and the organic layer was extracted with ether. After the ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 20%).
/ 1) and 0.45 g of 2,3-difluoro-4'-bis (12-benzyloxidedecyl) methoxybiphenyl (Y: 29
%). The purity of the obtained compound was 98.7% by HPLC.

(D) Synthesis of a compound represented by the following formula:

[0280]

Embedded image

In a 100 ml autoclave, 2,3-difluoro-
0.39 g of 4'-bis (12-benzyloxidedecyl) methoxybiphenyl, 0.5 g of 10% Pd-C, and 30 g of tetrahydrofuran
Then, the mixture was stirred at room temperature for 3 days with the hydrogen pressure set to 10 kg / cm ² . After the catalyst was filtered off and the filtrate was concentrated, the residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 1/1) to give 2,3-difluoro-4′-bis (12-hydroxy 0.23 g of (dodecyl) methoxybiphenyl (Y: 77%) was obtained. The purity of the obtained compound is H
It was 100% by PLC.

(E) Synthesis of the compound represented by the following formula:

[0283]

Embedded image

In a 50 ml flask, 2,3-difluoro-4'-bis
0.23 g of (12-hydroxydodecyl) methoxybiphenyl, 0.06 g of acrylic acid, 0.26 g of triphenylphosphine, and 20 ml of tetrahydrofuran were charged. 0.17 g of ethyl azodicarboxylate was added dropwise to this reaction system under ice-cooling, and the mixture was returned to room temperature and stirred for 2 hours. The reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 20/1) to give 2,3-difluoro-
0.14 g (Y: 51.4%) of 4'-bis (12-acryloyloxidedecyl) methoxybiphenyl was obtained. The obtained compound was liquid at room temperature. The purity of the obtained compound was 99% by HPLC.
%, One spot by TLC.

According to the result of IR measurement and the fact that a molecular ion peak was observed at 696 by Mass analysis,
In addition, from the relationship between the raw materials used, it was confirmed that the obtained substance was a compound represented by Chemical Formula 44.

Example 7 A polymerizable compound represented by the following formula was synthesized.

[0287]

Embedded image

The following shows the synthesis procedure.

(A) Synthesis of a compound represented by the following formula:

[0290]

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A 100 ml flask was charged with 0.44 g of lithium aluminum hydride and 50 ml of diethyl ether. To this reaction system, 5.4 g of ethyl 2,2-bis (6-benzyloxyhexyl) acetate obtained in Example 2- (d) was added dropwise under cooling with ice and water, and the mixture was returned to room temperature for 1 hour and refluxed. For 1 hour. The reaction solution was poured into cold diluted hydrochloric acid, the ether layer was washed with water, dried over sodium sulfate, and the solvent was distilled off. The residue is subjected to silica gel column chromatography (eluent:
Purified by toluene / ethyl acetate = 4/1) to give 2,2-
4.7 g of bis (6-benzyloxyhexyl) ethanol (Y: 9
6%). The purity of the obtained compound was 97.1% by GC.

(B) Synthesis of a compound represented by the following formula:

[0293]

Embedded image

A 200 ml flask was charged with 13.8 g of 2,2-bis (6-benzyloxyhexyl) ethanol, 10.2 g of triphenylphosphine, and 50 ml of methylene chloride. At room temperature, a solution of 16.1 g of carbon tetrabromide in methylene chloride 5 was added to the reaction system.
0 ml was added dropwise and stirred for 1 hour. The reaction solution was washed with an aqueous sodium hydrogen carbonate solution and water in that order, dried over sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: toluene) to give 2,2-
Bis (6-benzyloxyhexyl) ethyl bromide 11g
(Y: 69%). The purity of the obtained compound was 97.5 by GC.
%Met.

(C) Synthesis of a compound represented by the following formula:

[0296]

Embedded image

In a 300 ml flask, 6 g of 2,2-bis (6-benzyloxyhexyl) ethyl bromide, sodium iodide
2.19 g and 150 ml of 2-butanone were charged and stirred for 16 hours under reflux. The reaction solution was poured into water, and the organic layer was extracted with ether. The ether layer was washed with water and dried over sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography (eluent: toluene) to give 2,2-bis
6 g of (6-benzyloxyhexyl) ethyl iodide (Y: 9
1.2%). The purity of the obtained compound was 95.3% by HPLC.
Met.

(D) Synthesis of a compound represented by the following formula:

[0299]

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A 200 ml flask was charged with 6.4 g of pyridinium chlorochromate, 0.48 g of sodium acetate, and 10 ml of methylene chloride. This reaction was carried out at room temperature in Example 2-
50 ml of a methylene chloride solution of 6 g of 2,3-difluoro-4 '-(6-hydroxyhexyl) oxybiphenyl obtained in (f) was added dropwise, and the mixture was stirred for 18 hours. The reaction solution was concentrated, and the residue was purified by silica gel column chromatography (eluent: toluene), recrystallized from a mixed solvent of hexane / acetone, and 2,3-difluoro-4 '-(5-formylpentyl) oxybiphenyl 2.56 g (Y: 42.9%) was obtained. The purity of the obtained compound was 95.1% by GC.

(E) Synthesis of a compound represented by the following formula:

[0302]

Embedded image

A 100 ml flask was charged with 4.3 g of 2,2-bis (6-benzyloxyhexyl) ethyl iodide, 2.1 g of triphenylphosphine, and 50 ml of toluene.
After stirring for an hour, toluene was distilled off to obtain a phosphonium salt. Next, 30 ml of tetrahydrofuran was added to dissolve the phosphonium salt, and then, under ice-water cooling, 2,3-difluoro-
20 ml of a tetrahydrofuran solution of 1.93 g of 4 '-(5-formylpentyl) oxybiphenyl and then 1 g of potassium tert-butoxy were added, and the mixture was stirred at the same temperature for 4 hours, returned to room temperature and stirred for 24 hours. The reaction solution was poured into water, and the organic layer was extracted with ether. The ether layer was washed with water and dried over sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: toluene / hexane = 9/1) to give 2,3-difluoro-4. '-[8,8-Bis (6-benzyloxyhexyl) -6-octen-1-yl] oxybiphenyl
3.3 g (Y: 74.5%) was obtained. The purity of the obtained compound is HP
It was 98.9% by LC.

(F) Synthesis of the compound represented by the following formula:

[0305]

Embedded image

In a 200 ml autoclave, 2,3-difluoro-
4 '-[8, 8-bis (6-benzyloxyhexyl) -6-octene-
3.3 g of 1-yl] oxybiphenyl, 1 g of 10% Pd-C, and 100 ml of tetrahydrofuran were charged, and the hydrogen pressure was increased to 10 kg / cm ^2.
And stirred at room temperature for 2 days. After the catalyst was filtered off and the filtrate was concentrated, the residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 3/2) to give 2,3-difluoro-4 '-[8,8-. 2.3 g of bis (6-hydroxyhexyl) octyl] oxybiphenyl (Y: 93.6%)
I got The purity of the obtained compound was 98.8% by HPLC.

(G) Synthesis of the compound represented by the following formula:

[0308]

Embedded image

In a 100 ml flask, 2,3-difluoro-4 '-[8,
8-bis (6-hydroxyhexyl) octyl] oxybiphenyl 2.3 g, acrylic acid 0.8 g, triphenylphosphine 2.
9 g and 50 ml of tetrahydrofuran were charged. 1.93 g of ethyl azodicarboxylate was added dropwise to the reaction system under ice-water cooling, and the mixture was returned to room temperature and stirred for 2 hours. The reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (eluent: benzene) to give 2,3-difluoro-4 '-[8,8-
1.31 g (Y: 47.1%) of bis (6-acryloyloxyhexyl) octyl] oxybiphenyl was obtained. The obtained compound was liquid at room temperature. The purity of the obtained compound was determined by HPLC.
99.5% and one spot by TLC.

From the results of IR measurement, the fact that a molecular ion peak was observed at 627 (CI method) in Mass analysis, and the relationship between the raw materials used, the obtained substance was a compound represented by the above formula (50). Was confirmed.

Example 8 A liquid crystal display device using the polymerizable compound of the present invention was produced by mask pattern exposure. Hereinafter, the manufacturing method will be described.

First, two glass substrates each having a thickness of 1.1 mm and having ITO (a mixture of indium oxide and tin oxide, thickness: 50 nm) as a transparent electrode were opposed to each other, and a spacer having an average particle diameter of 5 μm was sandwiched therebetween. A cell with a maintained thickness was produced. On one surface of the fabricated cell, a photomask 3 having a light-shielding portion 31 and a light-transmitting portion 32 as shown in FIG. 21 was arranged. The light shielding portion 31 is provided so as to correspond to the pixel.

Next, in this cell, 0.65 g of isobornyl acrylate, 0.25 g of 1,4-butanediol diacrylate, as a resin composition for constituting a polymer (wall),
p- phenyl styrene 0.15 g, a polymerizable compound D0.15g shown in Table 2, the liquid crystal composition MLC-6419 (Merck; △ n = + 0.0977, n o = 1.4802, a chiral agent S-8
11 was added so that d / p = 0.25), and a mixture of 12.0 g of Irgacure 651 and 0.04 g of a photopolymerization initiator was uniformly mixed, followed by capillary injection to obtain a liquid crystal cell.

[0314]

[Table 2]

Thereafter, while applying a voltage of ± 3 V between the transparent electrodes, irradiation was performed at 80 ° C. for 8 minutes at 8 mW / cm ² under a high-pressure mercury lamp through which a parallel beam could be obtained through a photomask. (In this state, the ultraviolet rays are applied to the liquid crystal cell as a pattern having spatial regularity.) Then, with the voltage applied as it is, at a cooling rate of 10 ° C./hr, The liquid crystal cell was gradually cooled to 25 ° C. (the liquid crystal becomes a nematic state), and the resin composition was cured by continuously irradiating ultraviolet rays for 3 minutes.

When the liquid crystal cell after curing of the resin composition was observed with a polarizing microscope, as shown in FIG. 22, a liquid crystal region 20 substantially reflecting the shape of the light shielding portion of the photomask was formed.
Further, it was observed that the liquid crystal molecules were in an axially symmetric alignment state with the center of the liquid crystal region 20 as the central axis.

A polarizing plate was attached to the outside of each substrate of the liquid crystal cell so that the optical axes were orthogonal to each other, thereby producing a liquid crystal display device.

The evaluation of the electro-optical characteristics of the liquid crystal display element was carried out by using a liquid crystal characteristics evaluation system LCD-5000 (manufactured by Otsuka Electronics Co., Ltd.) with a polarizing plate parallel to both sides of an empty cell in which two glass substrates were bonded. The voltage-transmittance characteristics and the response speed of the liquid crystal cell were measured by using the cell prepared by disposing as a reference. Here, the response speed is defined as the time required for the light transmittance change by applying a voltage of 10 V to change by 90% from the initial transmittance, as the rising response speed τ _r (ms). Is the response time of the falling time τ _d (ms), which is the time required for 90% to change from the black state transmittance by τ _r + τ _d (ms).
Was evaluated. The steepness of the driving characteristics was evaluated as the absolute value α of the ratio (V ₉₀ / V ₁₀ ) of the voltages V ₁₀ and V ₉₀ at which the transmittance changes by 10% and 90% of the total transmittance change width.

Table 3 shows the measurement results of the electro-optical characteristics together with the results of Examples 9 and 12 to 15 and Comparative Examples 1 to 4 to be described later.

Further, the characteristics of the polymerizable compound were evaluated by a glass transition temperature and a heat storage test of the liquid crystal display device. Table 3 shows the evaluation results. The specific procedure of the measurement is as follows: E ′ (storage elasticity) at a measurement frequency of 1 Hz using a viscoelastic spectrometer (manufactured by Seiko Instruments Inc .; DMS210) in a tensile mode (tension module). Ratio tanδ (= E ") between E" (loss modulus) and E "(loss modulus).
Tg of the polymer film was defined as the temperature giving the maximum value of (/ E '; loss tangent). Furthermore, the lower limit temperature at which defective alignment occurs was examined by a heat storage test of the liquid crystal display device for 100 hours, and the relationship with Tg was considered.

[0321]

[Table 3]

Further, when the disclination line was examined, no disclination line was recognized.

Example 9 A liquid crystal display device was prepared in the same manner as in Example 8 except that the compounds shown in Table 2 were used as the polymerizable compound D, and the electro-optical characteristics were evaluated.
Table 3 shows the results. Further, when the disclination line was examined, no disclination line was recognized.

Example 10 A liquid crystal display device was prepared in the same manner as in Example 8 except that the compounds shown in Table 2 were used as the polymerizable compound D, and the disclination line was examined. No ligation lines were observed.

Example 11 A liquid crystal display device was prepared in the same manner as in Example 8 except that the compounds shown in Table 2 were used as the polymerizable compound D, and the disclination line was examined. No ligation lines were observed.

(Example 12) A liquid crystal display device using the polymerizable compound of the present invention was produced by insulator pattern exposure. Hereinafter, the manufacturing method will be described.

First and second substrates having ITO (50 nm) as a transparent electrode on a glass substrate (1.1 mm thick) were used. The first substrate has a predetermined resist material (OMR8).
3: patterning film 40 made of an insulating material as shown in FIG. Specifically, the patterning film 40 is formed by applying a resist material, baking,
It was formed by each of the steps of exposure, development, rinsing, and baking using the photomask 3. The patterning film 40 was formed so as to correspond to the non-pixel portion. On the other hand, the second substrate has a polyimide insulating film AL4552 (manufactured by Nippon Synthetic Rubber Co., Ltd.).
Was applied and rubbed (rubbing was unprocessed). The produced first and second substrates are opposed to each other, and 5
A cell having a constant cell thickness was produced by sandwiching a μm spacer. Next, in this cell, 0.6 g of isobornyl acrylate and neopentyl diacrylate were used as a photopolymerizable resin material for forming a polymer (wall).
0.3 g, p-methylstyrene 0.15 g, polymerizable compound E 0.15 g shown in Table 4 below, and liquid crystal composition MLC-64
19 (Merck: △ n = + 0.0977, n o = 1.4802, ones were added so that the chiral agent S-811 a d / p = 0.25) and 12.0 g, and a photopolymerization initiator Irgacure 651 0.04 g The mixed homogeneous mixture was vacuum-injected from under reduced pressure to produce a liquid crystal cell.

[0328]

[Table 4]

Thereafter, the temperature of the liquid crystal cell was maintained at 90 ° C.
In addition, while applying an effective voltage of 2.5 V: 60 Hz between the transparent electrodes, 6 mW / cm ² under a high pressure mercury lamp from the first substrate side.
The resin composition was cured by irradiating it with ultraviolet light for 8 minutes.

Next, with the voltage applied, the liquid crystal cell was cooled to 40 ° C. over 5 hours, returned to room temperature (25 ° C.), and then irradiated with ultraviolet rays by the same ultraviolet ray irradiation device to accelerate the curing. Was.

FIG. 25 schematically shows the result of observing the liquid crystal cell after curing the resin composition with a polarizing microscope. As is clear from FIG. 25, the polymer is provided in the portion where the resist patterning film is formed (that is, the non-pixel portion), the liquid crystal region 20 is in a mono-domain state in each area of the ITO region, and The liquid crystal molecules were formed so as to be axially symmetrically oriented. This means that when a liquid crystal cell obtained by fixing two polarizing plates orthogonal to each other is rotated, the liquid crystal region 20 is rotated.
It can be seen from the observation that the position of the schlieren pattern (quenching pattern) is constant, and only the surrounding polymer wall is observed to rotate.

A polarizing plate was attached to the outside of each substrate of the liquid crystal cell so that the optical axes were orthogonal to each other, thereby producing a liquid crystal display device having a liquid crystal region surrounded by polymer walls.

In the liquid crystal display device of this example, the reversal phenomenon as seen in the TN mode liquid crystal display device not using the polymerizable compound of the present invention (Comparative Example 1 described later) was not observed, and the widening at the time of voltage saturation was not observed. There is no increase in transmittance in the viewing angle direction. Further, no roughness was observed even in the halftone display state.

Example 13 A liquid crystal display device was prepared in the same manner as in Example 12 except that the compounds shown in Table 4 were used as the polymerizable compound E, and the electro-optical characteristics were evaluated. Table 3 shows the results.

FIG. 23 shows the voltage-transmittance characteristics of the obtained liquid crystal display device. This characteristic was substantially the same for the liquid crystal display devices obtained in the other examples.

Further, in the liquid crystal display device of this example, a TN mode liquid crystal display device not using the polymerizable compound of the present invention was used.
No reversal phenomenon as seen in (Comparative Example 1 described later) is observed, and no increase in transmittance in a wide viewing angle direction at the time of voltage saturation is observed. Further, no roughness was observed even in the halftone display state.

Example 14 A liquid crystal display device was prepared in the same manner as in Example 12 except that the compounds shown in Table 4 were used as the polymerizable compound E, and the electro-optical characteristics were evaluated. Table 3 shows the results.

In the liquid crystal display device of this example, the reversal phenomenon as seen in the TN mode liquid crystal display device not using the polymerizable compound of the present invention (comparative example 1 described later) was not observed, and the widening at the time of voltage saturation was not observed. There is no increase in transmittance in the viewing angle direction. Further, no roughness was observed even in the halftone display state.

Example 15 A liquid crystal display device was prepared in the same manner as in Example 12 except that the compounds shown in Table 4 were used as the polymerizable compound E, and the electro-optical characteristics were evaluated. Table 3 shows the results.

In the liquid crystal display device of this example, the reversal phenomenon as seen in the TN mode liquid crystal display device not using the polymerizable compound of the present invention (Comparative Example 1 described later) was not observed, and the widening at the time of voltage saturation was not observed. There is no increase in transmittance in the viewing angle direction. Further, no roughness was observed even in the halftone display state.

Example 16 A TN mode liquid crystal display device was produced using the polymerizable compound of the present invention. Hereinafter, the manufacturing method will be described.

A polyimide alignment film (AL455) was formed on a glass substrate (1.1 mm thick) having ITO (50 nm) as a transparent electrode.
2: Nippon Synthetic Rubber Co., Ltd.) was applied by spin coating, and then subjected to a predetermined rubbing treatment with a nylon cloth.
Two such substrates were produced. An average particle size of 5 μm is set so that the two rubbed directions are orthogonal to each other.
Were bonded via an LCD spacer.

The photomask shown in FIG. 21 was placed on the substrate thus bonded, and the same resin composition and liquid crystal material ZLI-4792 as in Example 13 were placed between the substrates.
(Manufactured by Merck: Δn = 0.094) and a photopolymerization initiator Irgacure65
A mixture obtained by mixing 1 with the same ratio as in Example 13 was injected by capillary injection. The following procedure was performed in the same manner as in Example 8 to produce a liquid crystal cell having a liquid crystal region surrounded by a polymer.

A TN mode liquid crystal display device was obtained by attaching a polarizing plate to this liquid crystal cell such that the polarization axis coincided with the rubbing direction.

The liquid crystal display device manufactured in this example had a TN alignment having a uniform alignment state. This liquid crystal display element showed no change in display characteristics even when the display surface was pressed with a pen or the like. That is, in this liquid crystal display device, the liquid crystal region is surrounded by a polymer, so that the conventional TN
It was confirmed that the pressure resistance of the mode liquid crystal display element (Comparative Example 1 described later) was significantly improved.

Example 17 An STN mode liquid crystal display device was produced using the polymerizable compound of the present invention. Less than,
The manufacturing method will be described.

On a glass substrate (1.1 mm thick) having ITO (50 nm) as a transparent electrode, a polyimide alignment film (Sun Ever:
(Nissan Chemical Co., Ltd.) was applied by a spin coating method, and then subjected to a predetermined rubbing treatment with a nylon cloth. Two such substrates were produced. The two prepared substrates were bonded via an LCD spacer having an average particle size of 9 μm so that the rubbing directions were 240 ° to each other.

A photomask shown in FIG. 21 is arranged on the substrates thus bonded, and a resin composition and a liquid crystal material ZLI-4427 similar to those in Example 13 are provided between the substrates.
Example 1 (Merck) and a photopolymerization initiator Irgacure651
The mixture mixed in the same ratio as 3 was injected by capillary injection. The following procedure was performed in the same manner as in Example 8 to produce a liquid crystal cell having a liquid crystal region surrounded by a polymer.

A polarizing plate was attached to this liquid crystal cell so that the polarization axis was at 45 ° from the rubbing direction and at 105 ° to each other, to obtain an STN mode liquid crystal display device.

The liquid crystal display device manufactured in this example had an STN alignment having a uniform alignment state. This liquid crystal display element showed no change in display characteristics even when the display surface was pressed with a pen or the like. That is, this liquid crystal display element
Since the liquid crystal region is surrounded by the polymer, the conventional S
It was confirmed that the pressure resistance of the device was dramatically improved as compared with the TN mode liquid crystal display device.

Example 18 Using the polymerizable compound of the present invention, an SSFLC mode liquid crystal display device was manufactured. Hereinafter, the manufacturing method will be described.

On a glass substrate (1.1 mm thick) having ITO (50 nm) as a transparent electrode, a polyimide alignment film (Sun Ever:
(Nissan Chemical Co., Ltd.) was applied by a spin coating method, and then subjected to a predetermined rubbing treatment with a nylon cloth. Two such substrates were produced. LCD having an average particle size of 2 μm so that the rubbing directions are orthogonal to each other.
They were bonded via a spacer.

A photomask shown in FIG. 21 was placed on the substrates thus bonded, and a polyethylene glycol diacrylate was used as a resin composition between the substrates.
(NK ester A-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.005
g, lauryl acrylate 0.13 g, styrene 0.01 g, and compound E of Example 13 0.05 g, and Z as a liquid crystal material.
0.80 g of LI-4003 (manufactured by Merck) and Irg photopolymerization initiator
A mixture with 0.005 g of acure651 was uniformly mixed, and then vacuum-injected under reduced pressure in a heated state. The following procedure was performed in the same manner as in Example 8 to produce a liquid crystal cell having a liquid crystal region surrounded by a polymer.

A polarizing plate is attached to this liquid crystal cell so that the polarization axes are at 90 ° to each other, and the liquid crystal cell is subjected to FLC mode (SSF mode).
Liquid crystal display device having a (type orientation).

The liquid crystal display device manufactured in this example had SSFLC alignment having a uniform alignment state. This liquid crystal display element showed no change in display characteristics even when the display surface was pressed with a pen or the like. Furthermore, no alignment disturbance due to an external force, which is a problem observed in a normal FLC mode liquid crystal display device, was confirmed. That is, in this liquid crystal display device, it was confirmed that the pressure resistance of the device was dramatically improved as compared with the conventional FLC mode liquid crystal display device because the liquid crystal region was surrounded by the polymer.

(Comparative Examples and Reference Examples) Hereinafter, comparative examples and reference examples effective for verifying the effects of the embodiments of the present invention will be described.

Comparative Example 1 A conventional TN mode liquid crystal display device was manufactured.

In the same manner as in Example 8, two substrates on which transparent electrodes were formed were bonded. The same liquid crystal material MLC-6419 (manufactured by Merck Co., Ltd., added with a chiral agent S-811 so that d / p = 0.25) was injected between the substrates to form a liquid crystal cell. A polarizing plate was attached to the outside of each substrate of the liquid crystal cell so that the optical axes were orthogonal to each other, thereby producing a conventional TN mode liquid crystal display device.

The electro-optical characteristics of the obtained liquid crystal display device were evaluated in the same manner as in Example 8. Table 3 shows the evaluation results. FIG. 26 shows the viewing angle characteristics of this liquid crystal display element.

(Comparative Example 2) In the same manner as in Example 8, two substrates each having a transparent electrode formed thereon were bonded to each other to produce a cell. On one surface of the fabricated cell, a photomask 3 having a light-shielding portion 31 and a light-transmitting portion 32 as shown in FIG. 21 was arranged. The light shielding portion 31 is provided so as to correspond to the pixel. In this cell, 0.65 g of stearyl acrylate, 1,
0.25 g of 4-butanediol diacrylate, 0.10 g of p-phenylstyrene, and 10 g of a liquid crystal material MLC-6419 (manufactured by Merck, added with a chiral agent S-811 so that d / p = 0.25) and 10 g of light Polymerization initiator Irgacure651 0.03
g and a homogeneous mixture were injected by capillary to produce a liquid crystal cell. The following procedure was performed in the same manner as in Example 12 to fabricate a liquid crystal cell having a liquid crystal region surrounded by a polymer.

Next, a polarizing plate was arranged in a crossed Nicols state and bonded to the manufactured liquid crystal cell to manufacture a liquid crystal display device. In the same manner as in Example 8, the electro-optical characteristics of the obtained liquid crystal display device were evaluated. Table 3 shows the evaluation results.

In the liquid crystal display device of this comparative example, the phase separation between the liquid crystal and the polymer was insufficient, and the presence of a resin material in the liquid crystal region was observed. Furthermore, the occurrence of disclination lines was observed when voltage was applied, which was not satisfactory in terms of display characteristics. The transmittance when applying 10V voltage is 2.
It was 0%. This value is larger than the values of the liquid crystal display elements of Examples 8 to 16, and is considered to be largely caused by the occurrence of disclination lines.

Reference Example 1 0.6 g of isobornyl acrylate, 0.3 g of neopentyl diacrylate as a resin composition
g, 0.15 g of p-methylstyrene, 0.15 g of a polymerizable compound Z shown in Table 5 below, and MLC-6419 as a liquid crystal composition (a chiral agent S-811 manufactured by Merck Ltd. was added so that d / p = 0.25). 12g, and a photopolymerization initiator Irgacure 651 0.
A liquid crystal display device was produced in the same manner as in Example 12, except that a homogeneous mixture with 04 g was used. In the same manner as in Example 8, the electro-optical characteristics of the obtained liquid crystal display device were evaluated. Table 3 shows the evaluation results.

[0364]

[Table 5]

Reference Example 2 A liquid crystal display device was produced in the same manner as in Reference Example 1, except that the compounds shown in Table 5 were used as the polymerizable compound Z. In the same manner as in Example 8,
The electro-optical characteristics of the obtained liquid crystal display device were evaluated. Table 3 shows the evaluation results.

According to a polarizing microscope observation of the liquid crystal display devices produced in Reference Examples 1 and 2, the addition of a polymerizable compound having a liquid crystal-like skeleton in the molecule suppressed the occurrence of disclination lines when voltage was applied. Was observed. Therefore, the transmittance when a 10 V voltage was applied was about 0.7%, which was a relatively good black state display.

As described above, although the liquid crystal display element of the reference example shows relatively good characteristics, a comparison between the liquid crystal display element of the embodiment of the present invention and the liquid crystal display element of the reference example shows that Was confirmed to have more excellent properties. This will be described below.

First, the heat-resistant upper limit temperature of the liquid crystal orientation of the polyfunctional polymer compound of the present invention is higher by about 15 to 20 ° C. than that of the linear monofunctional compound of the reference example. It can be seen that the use of the introduced polymerizable compound dramatically improves the heat resistance of the liquid crystal display device of the present invention.
(In addition, as is clear from Table 3, the glass transition temperature (Tg)
And, when examining the relationship between the lower limit temperature at which misalignment occurs by a heat storage test at 100 hours of the liquid crystal display element, the smaller the number of atoms in the bonding group portion, the higher the Tg, and the higher the heat resistance temperature. Is observed. Furthermore, when the transition temperature of the liquid crystal region of the liquid crystal display element was evaluated by a polarizing microscope, it was, for example, 83 ° C. in Example 12 and 68 ° C. in Reference Example 1. That is, it was confirmed that the use of the polyfunctional compound of the present invention was much closer to the transition temperature (87 ° C.) of the liquid crystal material alone. This means that the polyfunctional compound of the present invention has higher reactivity than the linear monofunctional compound of Reference Example, and is therefore more excellent from the viewpoint of the display characteristics of the liquid crystal display device. Is shown.

Further, the liquid crystal display device using the polyfunctional compound of the present invention and the liquid crystal display device using the linear monofunctional compound of the reference example were almost equivalent in electro-optical characteristics and display characteristics. .

As described above, the liquid crystal display device using the polymerizable compound of the present invention does not generate disclination lines, has little deterioration in response speed and voltage-transmittance characteristics, and is bright even when no voltage is applied. It was confirmed that it had high contrast and was excellent in strength and heat resistance.

[0371]

As is clear from the above description, the polymerizable compound of the present invention is a polyfunctional compound having a liquid crystal-like skeleton and having a branched polymerizable active group. The polyfunctional compound of the present invention easily forms a three-dimensional network structure,
And it has excellent reactivity. Therefore, the polyfunctional compound of the present invention maintains the properties of the conventional monofunctional “polymerizable compound having a liquid crystal-like skeleton”, and at the same time, reduces the deterioration of the characteristics of the liquid crystal display device due to the unreacted compound. However, the characteristics of the polyfunctional compound such as improvement of the glass transition temperature (Tg) of the polymer can be realized at the same time. Therefore, it is extremely effective from the viewpoints of display characteristics, strength (for example, pressure resistance, impact resistance) and heat resistance of the liquid crystal display element. In particular, in a liquid crystal display device formed using a liquid crystal-polymer composite, since the storage heat-resistant temperature and the operating temperature range of the device are dramatically improved, the polymerizable compound of the present invention is used for a liquid crystal display device. This is extremely effective from the viewpoint of heat resistance reliability. Furthermore, when the polymerizable compound of the present invention is used for a liquid crystal display device, generation of disclination lines when a voltage is applied is suppressed. Therefore, high-contrast display can be realized in the liquid crystal display device.

The polymerizable compound of the present invention also improves the separability between liquid crystal and resin material during production of a liquid crystal display element, suppresses the incorporation of resin material into the liquid crystal material, and combines polymer and liquid crystal molecules. Has the effect of lowering the anchoring on the surface, and is also effective for stabilizing the alignment of liquid crystal molecules.

Further, by using these polymerizable compounds in a liquid crystal display device, the deterioration of the response speed, the threshold characteristics of voltage-transmittance characteristics or the deterioration of steepness, which had been a problem in the past, are greatly improved. Is done. That is,
By using the polymerizable compound of the present invention, the display characteristics of the liquid crystal display element are improved. Such a liquid crystal display element is
It has the following features: (1) It has excellent viewing angle characteristics due to its axially symmetric alignment state, and has excellent impact resistance because it has a polymer wall in the cell. I have. Especially,
It can be widely applied to a large screen display, a pen input type liquid crystal display device, and the like. (2) In a liquid crystal display device in which the alignment regulating force on the substrate can be utilized in the liquid crystal region, the alignment state is made uniform and the pressure resistance against external pressure such as pen input is improved.

As described above, the liquid crystal display device of the present invention
Since the polymerizable compound having the effect of improving the alignment regulating force of the liquid crystal molecules is provided as a constituent, the axially symmetric alignment state of the liquid crystal molecules in the liquid crystal region becomes better than before. Therefore, the liquid crystal display device of the present invention is a display device having improved viewing angle characteristics and high display quality. Moreover, this liquid crystal display element is very excellent in heat resistance. Such a liquid crystal display element can be suitably used for a display (for example, a personal computer, a word processor, a liquid crystal television, and a display panel for car navigation) utilizing a wide viewing angle characteristic.

[Brief description of the drawings]

FIG. 1 is a view showing Synthesis Route 1 of a polymerizable compound of the present invention.

FIG. 2 is a diagram showing Synthesis Route 1 of the polymerizable compound of the present invention.

FIG. 3 is a diagram showing Synthesis Route 2 of the polymerizable compound of the present invention.

FIG. 4 is a diagram showing Synthesis Route 2 of the polymerizable compound of the present invention.

FIG. 5 is a diagram showing Synthesis Route 3 of the polymerizable compound of the present invention.

FIG. 6 is a diagram showing Synthesis Route 4 of the polymerizable compound of the present invention.

FIG. 7 is a diagram showing Synthesis Route 5 of the polymerizable compound of the present invention.

FIG. 8 is a diagram showing Synthesis Route 6 of the polymerizable compound of the present invention.

FIG. 9 is a diagram showing Synthesis Route 7 of the polymerizable compound of the present invention.

FIG. 10 is a view showing Synthesis Route 8 of the polymerizable compound of the present invention.

FIG. 11 is a view showing Synthesis Route 9 of the polymerizable compound of the present invention.

FIG. 12 is a diagram showing Synthesis Route 9 of the polymerizable compound of the present invention.

FIG. 13 is a view showing Synthesis Route 10 of the polymerizable compound of the present invention.

FIG. 14 is a view showing Synthesis Route 10 of the polymerizable compound of the present invention.

FIG. 15 is a view showing Synthesis Route 11 of the polymerizable compound of the present invention.

FIG. 16 is a view showing Synthesis Route 12 of the polymerizable compound of the present invention.

FIG. 17 is a diagram showing Synthesis Route 13 of the polymerizable compound of the present invention.

FIG. 18 is a diagram showing Synthesis Route 14 of the polymerizable compound of the present invention.

FIG. 19 is a diagram showing Synthesis Route 15 of the polymerizable compound of the present invention.

FIG. 20 is a diagram showing a synthesis route 16 of the polymerizable compound of the present invention.

FIG. 21 is a conceptual diagram of a photomask used in an example of the present invention.

FIG. 22 is a schematic view showing the result of observation of a liquid crystal cell of the liquid crystal display device of the present invention with a polarizing microscope.

FIG. 23 is a graph and a schematic diagram illustrating the electro-optical characteristics and the viewing angle characteristics of the liquid crystal display device of the present invention.

FIG. 24 is a schematic view of a substrate on which a patterning film is formed in the liquid crystal display device of the present invention. (A) is a top view,
(B) is BB 'sectional drawing of (a).

FIG. 25 is a schematic view showing an alignment state of a liquid crystal region in the liquid crystal display device of the present invention.

26A and 26B are a graph and a schematic diagram illustrating an electro-optical characteristic and a viewing angle characteristic of a TN mode liquid crystal display element of Comparative Example 1.

FIG. 27 is a schematic diagram illustrating a change in contrast depending on the viewing angle of a conventional TN mode liquid crystal display device.

FIG. 28 is a schematic diagram illustrating a change in contrast according to the viewing angle of a conventional wide viewing angle mode liquid crystal display device.

FIG. 29 is a schematic diagram illustrating a state of occurrence of a disclination line when a voltage is applied in a conventional liquid crystal display element.

[Explanation of symbols]

 Reference Signs List 1 substrate 3 photomask 10 liquid crystal layer 20 liquid crystal region 21 polymer wall 22 disclination line 30 pixel portion (photomask pattern) 31 photomask light shielding portion 32 photomask light transmitting portion 40 resist patterning film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G02F 1/1333 G02F 1/1333 1/1337 1/1337 // C07C 43/174 7419-4H C07C 43 / 174 43/225 7419-4H 43/225 D 43/23 7419-4H 43/23 E 47/457 8114-4H 47/457 49/697 8114-4H 49/697 (72) Inventor Masahiko Yoshida Soka, Saitama 1-7-1, Inari, Kanto Chemical Research Institute, Central Research Institute (72) Inventor Hoyo Mizobe 1-7-1, Inari, Soka City, Saitama Pref., Kanto Chemical Research Institute Central Research Institute (72) Inventor Kenji Suzuki 1-7-1 Inari, Soka City, Saitama Prefecture Kanto Kagaku Co., Ltd. Central Research Laboratory

Claims (8)

[Claims] 1. A polymerizable compound represented by the following formula (I): Wherein X is a hydrogen atom or a methyl group; l and m are each independently an integer from 0 to 14;
Is a single bond, -COO-, -OCO-, or -O-; n and p are each independently an integer from 0 to 18; q and s are each independently 0 or 1; R ^A
And R ^B are each independently a group represented by formula (II) or (I
II): embedded image However, when q = 1, p ≧ 2; when R ^A is represented by the formula (II), R ^B is represented by the formula (II). 2. The polymerizable compound according to claim 1, wherein in the formula (I), n + p ≦ 18. 3. The polymerizable compound according to claim 1, wherein in the formula (I), n + p ≦ 18 and s = 0. 4. The polymerizable compound according to claim 1, wherein in the formula (I), n + p ≦ 18 and s = 1. 5. A liquid crystal display device in which a liquid crystal layer having a polymer and a liquid crystal region surrounded by the polymer is sandwiched between a pair of substrates, wherein the polymer is a liquid crystal display. A liquid crystal display device formed from a polymerization precursor containing at least the polymerizable compound according to any one of the above. 6. The liquid crystal display device according to claim 5, wherein the alignment state of the liquid crystal molecules in the liquid crystal region is an axially symmetric, radial or concentric alignment, a spiral alignment, or a random alignment. 7. The liquid crystal display device according to claim 5, further comprising an insulating film on the substrate for regulating an alignment state of liquid crystal molecules. 8. An insulating alignment film for realizing a uniaxially uniform alignment state of liquid crystal molecules corresponding to the liquid crystal region on the substrate, wherein the alignment state of the liquid crystal region is The liquid crystal display element according to claim 5, wherein an entire configuration of the element is arranged suitable for TN, STN, ECB, and SSFLC modes.