JP2599917B2 - Manufacturing method of liquid crystal optical element - Google Patents

Description

The present invention relates to a method for manufacturing a liquid crystal optical element suitable for a large-area liquid crystal display element, a liquid crystal storage element, and the like.

[Conventional technology]

Conventionally, to display a large area, a method of stacking small blocks such as a CRT and a fluorescent display tube to increase the area (such as astrovision) has been known, but the driving method is complicated and requires a huge number of devices. And In addition, such a method of arranging small blocks is not suitable for a high-resolution display because a connection portion is formed, and has a drawback that it is not suitable for displaying a continuous pattern.

Therefore, recently, a liquid crystal optical element capable of displaying a large area using a polymer liquid crystal has been studied (for example, JP-A-59-10930 and JP-A-61-1).
No. 37133).

However, the conventional technique proposed in Japanese Patent Application Laid-Open No. 59-10930 has basic problems such as lack of responsiveness in an electric field and contrast, and on the other hand, Japanese Patent Application Laid-Open No. 61-137133. The liquid crystal optical element comprising a stretch-oriented polymer liquid crystal described in the publication, in terms of responsiveness and contrast, although an improvement effect is recognized as such, since an orientation treatment by a stretching method is used,
It is difficult to produce a thin alignment film having a thickness of 5 μm or less. The alignment ability is low for polymer liquid crystals with short spacer lengths such as methylene chains and ether chains, and it is difficult to stretch with polymer liquid crystals having a relatively low degree of polymerization, and the liquid crystal materials used are limited. There were problems such as the necessity of a two-stage process of film-> orientation.

[Problems to be solved by the invention]

The present invention has been made based on the above circumstances,
The purpose is to solve the above problems, to have a highly oriented polymer liquid crystal alignment film effective for improving electric field responsiveness and contrast, and to be able to be manufactured in a simple process under mild conditions. An object of the present invention is to provide a method for manufacturing a liquid crystal optical element having excellent advantages.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a liquid crystal optic comprising a polymer liquid crystal obtained by a specific film forming method in which at least one sheet is sandwiched between transparent conductive films. The element has a highly oriented alignment film, the electric field responsiveness and the contrast are remarkably improved, it can be used advantageously as a large screen or a curved screen, etc., and in a simple process under mild conditions The inventors have found that they have advantages such as easy production, and have completed the present invention.

That is, in the present invention, at least one sheet is transparent.
When manufacturing a liquid crystal optical element comprising a polymer liquid crystal film sandwiched between a plurality of conductive films, supplying a polymer liquid crystal on the conductive film,
On the supplied polymer liquid crystal, a coating rod is applied to the polymer liquid crystal so that a linear pressure of 0.5 to 100 kg / m is applied to the polymer liquid crystal.
An object of the present invention is to provide a method for producing a liquid crystal optical element, in which a polymer liquid crystal film is formed by simultaneously performing coating and alignment by moving at a speed of 1000 mm / sec.

Hereinafter, a method for manufacturing the liquid crystal optical element of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a cross-sectional view showing one embodiment of a liquid crystal optical element obtained according to the present invention. Sandwiched between the two conductive films 2 and 2 ′,
One of the two conductive films, for example, conductive film 2
Is provided on the substrate 3 in advance, and the other one, that is, the conductive film 2 ′ in this case, is provided on the surface of the polymer liquid crystal application alignment film 1 by direct evaporation or the like. (In this case, the substrate 3 'may be provided as shown in the drawing or may be used without providing it), or may be provided on the substrate 3' in advance.

One of the important points in the present invention is that at least one of the conductive films 2 and 2 'is a transparent conductive film.

As the transparent conductive film, an ordinary one can be used. For example, a NESA film on which tin oxide is adhered, an ITO film made of tin oxide and indium oxide, and the like can be preferably used. The transparent conductive film is preferably provided inside a transparent substrate of glass or plastic (polymethyl methacrylate, polycarbonate resin, or the like). When the liquid crystal optical element of the present invention is used as a display element, it is preferable to provide a polarizing plate or a reflecting plate outside the transparent substrate.

Examples of the opaque conductive film used when a transparent conductive film is not used include a deposited film of aluminum and metal, a sputtering film, and the like.

As the substrate 3 or the substrate 3 ′, a normal substrate such as a glass substrate, a resin substrate or a film can be used, but the substrate used in contact with at least one transparent conductive film is an optical display. A transparent substrate is used for the purpose of use as an element.

Although FIG. 1 shows that the polymer liquid crystal alignment film has one layer, the liquid crystal optical element of the present invention may be further configured as a multi-layered element as desired.

Next, the polymer liquid crystal used as the base material of the polymer liquid crystal alignment film 2 and the film forming alignment method by the coating method will be described in detail.

Polymer Liquid Crystal The polymer liquid crystal used in the present invention is not particularly limited, and various types can be used. In general, a polymer compound having a mesogen in a side chain via a spacer can be suitably used.

This side-chain type polymer liquid crystal is composed of three parts of a polymer main chain, a mesogen and a spacer, and examples thereof include those represented by the following general formula [1].

However, in [1] wherein the _E a E _'b is a polymeric backbone, D is a spacer, M is Mesonigen. b may be 0. When b is not 0, the (EDM) unit and the (E ′) unit may be linked by blocks, may be randomly linked, or may be linked alternately.

As the main chain, various polymer main chains can be used,
Preferred main chains include polyacrylate, polysiloxane, polyether, and polymethacrylate.

The spacer can be used various ones, for example, the following (2) _{formula, - (COO) m - (} CH 2) n - [2] (where [2] In the formula, m is 0 Alternatively, 1 and n represent an integer of 3 to 30).

As the mesogen M, various types can be used. For example, those represented by the following formula [3] can be suitably used.

~ (Z) ₁ -T ¹ [3] wherein 1 represents 0 or 1, Z represents 0 (oxygen atom), and T ¹ represents (However, G in the above formula is, for example, -COO-, -OCO-
And T ² is, for example, -COOT ³ , -OCOT ³ , -OT ³ , -C
OT ³ , represents -T ³ , wherein T ³ is, for example, an alkyl group,
It represents a halogen atom such as -Cl and -F, -CN, a chloroalkyl group, a fluoroalkyl group, and a cyanoalkyl group. ) Can be suitably used.

Among these polymer liquid crystals, a ferroelectric polymer liquid crystal is preferable in terms of electric field response speed, contrast, and the like, and a ferroelectric polymer liquid crystal having a chiral smectic C phase is particularly preferable.

Examples of the ferroelectric polymer liquid crystal having such a chiral smectic C phase include the following polymer liquid crystals (1) to (5). In addition, these (1)
The polymer liquid crystals of (5) generally have a chiral smectic C phase in a temperature range from room temperature to about 150 ° C., and are remarkably excellent in response speed, contrast and film formability.

(1) Polyacrylate polymer liquid crystal Polyacrylate polymer having a repeating unit represented by the following general formula and a copolymer thereof (Where k is an integer from 1 to 30, preferably an integer from 4 to 20, and R ¹ is Wherein R ² is -COOR ³ , OCOR ³ , -OR ³ , or -R ³ , wherein R ³ is And the like, where R ⁴ is -CH ₃ , -CN,
F or Cl, preferably CH ₃ , and m is from 0 to 10
And n is an integer of 0 to 10 (provided that R ⁴ is -CH ₃
When n is n is not 0. ). As R ^3, a particularly preferred, Can be mentioned.

(2) Polysiloxane-based polymer liquid crystal Polysiloxane-based polymer having a repeating unit represented by the following general formula and a copolymer thereof (In the formula, R ⁵ represents a lower alkyl group, p represents an integer of 3 to 30, and R ¹ has the same meaning as described above.) (3) Polyether polymer liquid crystal A repeating unit represented by the following general formula -Containing polyether polymers and their copolymers (In the formula, k and R ¹ have the same meanings as described above.) (4) Polyester-based polymer liquid crystal A polyester-based polymer having a repeating unit represented by the following general formula and a copolymer thereof (Wherein R ⁶ is H, CH ₃ or C ₂ H ₅ , l is an integer of 1 to 20,
k and R ¹ have the same meaning as described above. (5) High-molecular liquid crystal in which side chains are fixed to the main chain by hydrogen bonding.

The number average molecular weight of the polymer liquid crystal used in the present invention as described in (1) to (5) above is preferably from 2,000 to 40.
It is 0,000. If it is less than 2,000, there may be a problem with the polymer liquid crystal and the moldability as a coating film, while, on the other hand, 400,000
Exceeding the above may cause undesirable effects such as a slow response speed. The particularly preferred range of the number average molecular weight cannot be unconditionally defined because it depends on the type of the substituent and the like, but is 3,000 to 200,000.

In addition, these polymer liquid crystals may be used in combination of two or more as appropriate as long as the object of the present invention is not hindered.

The liquid crystal polymer according to the present invention is a liquid crystal polymer and an olefin resin, an acrylic resin, a methacrylic resin, a polystyrene resin, a polyester resin, and a polycarbonate resin, as long as the object of the present invention is not hindered. , Styrene-butadiene copolymer, vinylidene chloride
It is also possible to form a polymer liquid crystal film by using it by mixing with a normal resin such as an acrylonitrile copolymer.
However, when these resins are added in a large amount, the liquid crystallinity is deteriorated.

On the other hand, ferroelectric low-molecular liquid crystal,
For example, p-decyloxybenzylidene-p-amino-
A liquid crystal compound having a chiral smectic C phase such as 2-methylbutyl cinnamate may be used as a mixture. The mixing ratio is preferably 5 or less by weight.

There is no particular limitation on the method of blending the above components, and they can be blended by a usual method.

According to the method of the present invention, the polymer liquid crystal as described above,
Liquid crystal optics which is remarkably excellent in practical use by coating on a transparent conductive film or an opaque conductive film under specific conditions and performing film forming alignment treatment to form an alignment film, and sandwiching at least one of the transparent conductive films. An element can be obtained.

Production of Polymer-Coated Alignment Film Hereinafter, the polymer liquid crystal-coated alignment film 2 used in the present invention
An example of a specific manufacturing method will be described in detail with reference to the drawings.

FIG. 2 is a cross-sectional view showing a state of a coating process showing one embodiment of a method of applying a polymer liquid crystal in a manufacturing process of the liquid crystal optical element of the present invention. In the figure, 5 is a coating rod for coating and orienting the polymer liquid crystal material 6 on the substrate 3 having the conductive film 2 to form the polymer liquid crystal coating and alignment film 1; is there.

The shape of the application rod 5 is not particularly limited, but usually, a cylindrical roller or a spatula-shaped rod is suitably used. The application rod may be heated if desired.

In the coating method of FIG. 2, the coating film is formed by moving or reciprocating the coating rod 5 with respect to the substrate 3 and the fixed base 4 at a speed v. Here, the speed v is preferably in the range of 1 to 1000 mm / sec, preferably 5 to 600 mm / sec. The load w is given to the polymer liquid crystal material 6 or its alignment film 1 by the application rod 5. The load w is preferably in the range of 0.5 to 100 kg / m, preferably 1 to 30 kg / m, as a linear pressure.

Further, the polymer liquid crystal 6 and the polymer liquid crystal coating alignment film 1
Are heated by the fixing table 4. The temperature is set so as to be in a temperature range in which a liquid crystal state such as a mixed phase of a smectic A phase and an isotropic phase, a smectic A phase, or a chiral smectic C phase is maintained, and a temperature range lower than a clearing point. In order to perform this temperature adjustment, it is preferable that the heating device of the fixed base 5 be provided with a temperature controller.

The polymer liquid crystal material 6 is desirably used as a fluid or a semi-fluid having a viscosity range that facilitates formation of a coating film by adding an appropriate solvent or the like to the polymer liquid crystal.

The solvent used is not particularly limited as long as it does not interfere with the object of the present invention, but the solvent used is volatilized and removed by heating in the above-mentioned film forming step. Is preferred.

If desired, additives such as a viscosity-imparting material, a binder, and a plasticizer may be appropriately added to the polymer liquid crystal material.

The thus-obtained polymer liquid crystal coating alignment film 1 having a substrate with a conductive film on one side is, as shown in FIG.
A conductive film 2 ′ is provided directly on the surface by vapor deposition or the like, and is further sandwiched by using a substrate 3 ′ or a substrate 3 ′ having a conductive film 2 ′ in advance, if desired.
It can be finished as a liquid crystal optical element as shown in FIG.

Further, the liquid crystal coating alignment film 1 of the present invention can be suitably formed by the following coating method.

FIG. 3 is a sectional view showing an outline of the state of the coating step. In FIG. 3, the polymer film 7 with a transparent conductive film is continuously transferred at a speed v from a roll 10 by a take-up roll of a polymer liquid crystal element. The polymer liquid crystal material 6 is extruded and compressed by a load w with the application rods 9 and 9 ′ to form the polymer liquid crystal application alignment film 1, and the conductive film moving from the roller 12 on the surface of the alignment film 1. The film-attached polymer film 8 was laminated and adhered using the laminating roller 13, and at least one of the films was sandwiched between conductive film-attached polymer films (7 and 8) which were transparent conductive films with a transparent polymer film. As a liquid crystal optical element comprising a polymer-coated alignment film, it is sent to the next step by a feed roller.

Here, the moving speed v and the load w can be set in the above ranges.

The application rods 9 and 9 ′ may be roller-shaped rotating bodies or fixed bodies of various shapes such as roller-shaped and spatula-shaped rods.

Further, the rollers such as the coating rod 9 or 9 'and the overlapping roller 13 may be heated as desired, as described above.

The polymer film used in the method of FIG. 3 is not particularly limited, but is preferably a film having flexibility, and at least one of the films is a transparent polymer film having a transparent conductive film as described above. As such a transparent polymer film, for example, polyester, polycarbonate, polyether sulfone resin and the like can be suitably used.

The temperature as a condition for performing this film deposition and lamination is as follows:
The temperature can be set in the temperature range of the method shown in FIG.

This heating promotes the alignment of the polymer liquid crystal, and the solvent used can be volatilized and removed, and the adhesive lamination can be performed effectively.

By using the method illustrated in FIG. 3, the production line of the liquid crystal optical element according to the production method of the present invention can be easily made continuous, and a large-area screen or a flexible screen can be advantageously formed. Can be mass-produced.

By the method as described above, the production method of the present invention can be suitably performed.

The film thickness of the polymer liquid crystal application alignment film in the liquid crystal optical element obtained by appropriately adjusting the film forming conditions such as the moving speed v and the load w can be adjusted to a wide range. It is also possible to provide a liquid crystal optical element having a polymer liquid crystal alignment film of 5 μm or less, which has been difficult in the alignment method.

As described above, the liquid crystal optical element obtained by film-forming alignment by the coating method of the present invention has a highly-aligned polymer liquid crystal film, and the electric field response and contrast are significantly improved. As described above, when a ferroelectric polymer liquid crystal having a chiral smectic C phase is used as the polymer liquid crystal, the liquid crystal has excellent electric field responsiveness and contrast, and can be used not only as a normal optical element but also as a moving image element. Can be suitably used, and since the characteristics of the polymer liquid crystal are utilized, it can be suitably used as an optical element as a large-area screen, a curved screen, and the like. As mentioned above, it can be manufactured by extremely simple manufacturing process and mild conditions using a specific film forming method of performing film formation and orientation simultaneously. Significantly it is advantageous liquid crystal optical element, an optical display element, or as an optical storage display can be suitably used in the field of various optoelectronic.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

The structure of the obtained polymer or compound was determined by NMR, I
R was confirmed by elemental analysis, and the phase transition temperature was measured and the phase was confirmed by DSC and a polarizing microscope, respectively. Further, the electric field response speed and the contrast ratio were measured as follows.

Measurement of electric field response speed-Response time described in Production Examples 1 to 7-The obtained polymer liquid crystal was subjected to uniaxial stretching orientation treatment (stretching ratio 250%) at 60 to 100 ° C and 1 cm / sec, and a film thickness of 5 to 10 µm Of ITO film, which was previously patterned on an ITO substrate (20 × 1
0mm), and an AC electric field E =
4 × 10 ⁶ V / m was applied and the change in transmitted light amount (0 → 90
%) Response time was measured.

Measurement of Contrast Ratio A cell composed of the obtained polymer liquid crystal was sandwiched between orthogonal polarizers, and the ratio of transmitted light intensity when the applied electric field was inverted was measured.

The phase states are indicated using the following abbreviations. (Cry: Crystal, Iso:
Isotropic liquid, SmA: smectic A phase liquid crystal state, SmC: smectic C phase liquid crystal state, N: nematic phase, N ^* : chiral nematic phase, SmC ^* : chiral smectic C phase liquid crystal state, S ₁ : smectic which is difficult to identify (Liquid crystal state, G: glassy state) The numbers represent the phase change temperature in ° C.

In this example, the ferroelectric polymer liquid crystals (I to VII) obtained in Production Examples 1 to 10 or the non-ferroelectric polymer liquid crystals (VIII to IX) were used as the polymer liquid crystals.

Production Example of Polymer Liquid Crystal Production Example 1 (Production of Polymer Liquid Crystal I) Polymer liquid crystal compound having a repeating unit represented by the following general formula (1) Synthesis of acrylic acid 12-bromododecyl ester Acrylic acid 0.21 mol (14.8 g) and tetramethylammonium hydroxide (pentahydrate) 0.23 mol (41.8 g) were added to DMF.
After stirring in 300 ml for 2 hours to obtain a homogeneous solution, 0.21 mol (77.4 g) of 1,12-dibromododecane was added, and the mixture was further stirred for 10 hours. Next, water 300 was added to the reaction solution, and the mixture was extracted with ether and purified by column chromatography to obtain 24.6 g of the desired bromoester (1a) (yield 37).
%).

(2) Synthesis of p-hydroxybenzoic acid 2-methylbutyl ester 0.29 mol (40.0 g) of p-hydroxybenzoic acid and (S)
0.35 mol (30.9 g) of-(-)-2-methylbutanol was refluxed in 150 ml of toluene for 20 hours in the presence of 1 ml of concentrated sulfuric acid. The reaction solution was concentrated and then purified by column chromatography to obtain 53.2 g (yield: 88%) of p-hydroxybenzoic acid 2-methylbutyl ester [▲ [α] ²³ _D ▼ = + 4.95 ゜ (CHCl ₃ )]. Obtained.

(3) Synthesis of 4-carbobenzoxyoxybenzoic acid 65 mmol of carbobenzoxycyclolide (55 mmol (7.6 g) of p-hydroxybenzoic acid and 65 mmol (2.6 g) of sodium hydroxide) in 200 ml of water at ice temperature. 10.6 g) was added dropwise. After 24 hours, the precipitate was washed with water, filtered, dried, purified by column chromatography, and 15.0 g of 4-carbobenzoxyoxybenzoic acid (99% yield, mp 181.9 to 183.
1 ° C.).

(4) Synthesis of 4-carbobenzoxyoxybenzoic acid chloride Ether of 27 mmol (7.3 g) of 4-carbobenzoxyoxybenzoic acid and 27 mmol (5.6 g) of phosphorus pentachloride
The 50 ml solution was stirred at room temperature for 24 hours. After the reaction, the reaction mixture was deethered, and the crystals were recrystallized from hexane. 4.5 g of 4-carbon benzoxyoxybenzoic acid chloride (57% yield, mp
65.5-67.4 ° C).

(5) Synthesis of 4- (4'-carbonbenzoxyoxybenzoyloxy) benzoic acid 2-methylbutyl ester A solution of 16 mmol (3.3 g) of p-hydroxybenzoic acid 2-methylbutyl ester in 20 ml of THF and 40 ml of pyridine was prepared. After cooling, a solution of 10 mmol (2.9 g) of 4-carbobenzoxyoxybenzoic acid chloride in THF was added dropwise. The temperature was gradually returned to room temperature and stirred for 8 hours. After the reaction, the mixture was extracted with ether, concentrated, and then purified by column chromatography to obtain 2- (4'-carbobenzoxyoxybenzoyloxy) benzoic acid 2-methylbutyl ester (2.9 g, yield).
63%, mp 64.4-65.4 ° C.).

(6) Synthesis of 4- (4'-hydroxybenzoyloxy) benzoic acid 2-methylbutyl ester 6 mmol (2.8 g) of 4- (4'-carbonbenzoxyoxybenzoyloxy) benzoic acid 2-methylbutyl ester described above , 0.5g palladium carbon (5% catalyst)
Was reacted in a hydrogen gas atmosphere for 4 hours. After the reaction, palladium carbon was filtered through a membrane filter, concentrated and purified by column chromatography, and 4- (4'-hydroxybenzoyloxy) benzoic acid 2-methylbutyl ester 1.26 g (yield 64%, m.p.
p. 90.8-92.6 ° C).

(7) Synthesis of 4- [4 '-(12-acryloyloxidedecyloxy) benzoyloxy] benzoic acid 2-methylbutyl ester The above bromo ester (1a) 3.9 mmol (1.2 g)
And 3.3 mmol (1.1 g) of 2-methylbutyl ester of 4- (4'-hydroxybenzoyloxy) benzoic acid described above.
And potassium carbonate 15 mmol (2.1 g) in acetone
Refluxed for hours. After the reaction, the mixture was filtered, concentrated, purified by column chromatography, recrystallized with ethanol, and the desired monomer (3a) [▲ [α] ²³ _D ▼ = + 2.1
0.9% (1% (CHCl ₃ )) (53% yield).

(8) Synthesis of polymer Monomer (3a) 1.1 mmol (0.6
g), 0.26 mg of AIBN and 2 ml of dry THF were added, and the mixture was frozen and degassed, and then reacted at 60 ° C. for 15 hours. After cooling, the reaction product was concentrated, diluted with chloroform (20 ml / g), and purified by high performance liquid chromatography to obtain 0.3 g of the desired polymer liquid crystal compound I (conversion rate: 50%, Mn = 5,300). .

The phase transition behavior of the above polymer liquid crystal I was as follows.

Electric field response speed Response time: 0.02 seconds (10 ° C) Production Example 2 (Production of polymer liquid crystal II) Polymer liquid crystal compound having a repeating unit represented by the following general formula (1) Synthesis of acrylic acid 12-bromododecyl ester Acrylic acid 0.21 mol (14.8 g) and tetramethylammonium hydroxide (pentahydrate) 0.23 mol (41.8 g) were added to DMF.
After stirring in 300 ml for 2 hours to obtain a homogeneous solution, 0.21 mol (77.4 g) of 1,12-dibromododecane was added, and the mixture was further stirred for 10 hours. Next, water 300 was added to the reaction solution, and the mixture was extracted with ether and purified by column chromatography to obtain 24.6 g of the desired bromoester (1a) (yield 37).
%).

(2) Synthesis of 4'-hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester 93 mmol (20 g) of 4'-hydroxybiphenyl-4-carboxylic acid and 467 mmol of (S)-(-)-2-methylbutanol (41 g) was refluxed in 150 ml of benzene in the presence of 2 ml of concentrated sulfuric acid for 25 hours. Next, after concentrating the reaction solution, it was recrystallized from a mixed solvent of toluene and hexane to give a hydroxyester compound (2) [mp.
²³ _D ▼ = + 4.35 ° (CHCl _3)] to give 26.0g (98% yield).

(3) 4 '-(12-acryloyloxide desiloxy)
Synthesis of biphenyl-4-carboxylic acid 2-methylbutyl ester 15.8 mmol (5.0 mmol) of the above bromoester (1a)
g), a mixture of 14.2 mmol (4.0 g) of the above hydroxyester (2) and 56.8 mmol (7.9 g) of potassium carbonate was refluxed in acetone for 16 hours. The reaction solution was filtered and concentrated, and then recrystallized from ethanol to obtain 3.7 g of the desired monomer (2a) (▲ [α] ²³ _D ▼ = + 2.79 ゜ (CHCl ₃ ))
(50% yield).

(4) Synthesis of polymer 1.15 mmol (600 mg) of the monomer (2a) in 4 ml of THF
The reaction was carried out at 60 ° C. for 14 hours using 2.5 mg of AIBN as a polymerization initiator. The polymerization reaction product is purified by column chromatography, and 490 mg of the desired polymer liquid crystal compound (conversion rate: 8
2%, Mn = 6,500).

The phase transition behavior of the polymer liquid crystal II was as follows.

Phase transition behavior Electric field response speed Response time: 0.03 seconds (35 ° C.) Production Example 3 (Production of polymer liquid crystal III) Polymer liquid crystal compound having a repeating unit represented by the following general formula Preparation of Polymer Liquid Crystal III (1) Synthesis of 10-Chloro-1-decene To 26.0 g of 9-decene-1-ol, 10 drops of pyridine were added and placed in an eggplant flask. Under ice cooling, thionyl chloride 24.0
g was added dropwise. After the addition, the reaction was performed at 70 ° C. for 8.5 hours. After the reaction, the reaction mixture was diluted with dichloromethane and washed with an aqueous potassium carbonate solution. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure. The residue is purified by column chromatography,
27.7 g of 10-chloro-1-decene were obtained. (Yield 95%) (2) Synthesis of 4'-decenyloxybiphenyl-4-carboxylic acid 2-methylbutyl ester 2.5 g of 10-chloro-1-decene obtained in (1) and 6.5 g of sodium iodide Was dissolved in 2-butanone and stirred at 80 ° C. for 17 hours. After the reaction, the mixture was diluted with dichloromethane and washed with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. 4′-Hydroxybiphenyl-4-carboxylic acid 2-methylbutyl ester obtained in (2) of Example 2 was added to the residue.
4.8 g, potassium carbonate 2.4 g, 80 ° C. in 2-butanone
For 20 hours. After the reaction, inorganic substances were removed by filtration, and the mixture was concentrated under reduced pressure, and then purified by column chromatography to obtain 4.6 g of the desired biphenyl derivative.
(Yield: 76%) (3) Oxiranation 3.0 g of the biphenyl derivative obtained in (2) and 1.5 g of m-chloroperbenzoic acid were dissolved in dichloromethane, the system was replaced with argon, and the mixture was stirred at room temperature for 1 day. After the reaction, the resultant was washed with an aqueous potassium carbonate solution and further washed with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 3.0 g of the desired monomer represented by the following formula. (97% yield) (4) Synthesis of polymer 0.5 g of the monomer obtained in (3) was dissolved in 5 ml of dichloromethane, and the system was replaced with argon. 0.015 g of stannic chloride was added, and a polymerization reaction was carried out at room temperature for 6 days. After the reaction, the reaction solution was poured into methanol. The resulting precipitate is purified by repeating reprecipitation, and the desired polymer liquid crystal III 0.4 g (80% conversion,
_Mn = 2,800).

The phase transition behavior of the polymer liquid crystal III was as follows.

Electric field response speed Response time: 0.03 seconds (30 ° C) Production Example 4 (Production of polymer liquid crystal IV) Polymer liquid crystal compound having a repeating unit represented by the following general formula (1) 4- (7-octenyloxy) biphenyl-
Synthesis of 4'-carboxylic acid 2-methylbutyl ester 5.1 g of 8-bromo-1-octene, 4-hydroxybiphenyl-4'-carboxylic acid 2-methylbutyl ester 8.
2 g and 4.0 g of potassium carbonate were refluxed in acetone for 20 hours. After the reaction, dichloromethane was added for dilution, and inorganic substances were removed by filtration. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 8.1 g of 4- (7-octenyloxy) biphenyl-4'-carboxylic acid 2-methylbutyl ester (77% yield).

(2) Synthesis of polymer 4- (7-octenyloxy) biphenyl-4'-carboxylic acid 2-methylbutyl ester obtained in (1) 4.
0 g and polymethylhydrosiloxane (Aldrich, n
_D = 1.3799, d = 1.006, Mn = 2,900) 0.5 g of toluene 5
Dissolved in 0 ml. 5 mg of chloroplatinic acid hexahydrate was added as a catalyst and reacted at 80 ° C. for 24 hours under an argon atmosphere.
After the reaction, reprecipitation was performed in methanol. After drying the obtained polysiloxane under reduced pressure, it was dissolved in dichloromethane,
Washed with water. After the dichloromethane phase was collected and dried over magnesium sulfate, dichloromethane was distilled off under reduced pressure to obtain 2.1 g of the desired polymer liquid crystal compound. (Mn = 15,000) The phase transition behavior of this polymer liquid crystal V was as follows.

Electric field response speed Response time: 0.2 seconds (80 ° C) Production Example 5 Polymer liquid crystal compound having a repeating unit represented by the following general formula (1) 4- (7-hexenyloxy) biphenyl-
Synthesis of 4'-carboxylic acid 2-methylbutyl ester In place of 8-bromo-1-octene used in Example 4 (1), 4.7 g of 6-bromo-1-hexene was used. Using the same substance as in (1), namely, 6.3 g of 4-hydroxybiphenyl-4'-carboxylic acid 2-methylbutyl ester and 3.1 g of potassium carbonate, the same operation as in Example 4 was carried out to obtain the above 4- (7- Hexenyloxy)
6.4 g of 2-methylbutyl biphenyl-4'-carboxylic acid was obtained (79% yield).

(2) Synthesis of polymer 4- (7-hexenyloxy) biphenyl-4'-carboxylic acid 2-methylbutyl ester obtained in (1) 4.
0 g and 0.6 g of the polymethylhydrosiloxane used in Example 4 (2) were dissolved in 20 ml of toluene. 2 mg of chloroplatinic acid hexahydrate as a catalyst was added, and the mixture was heated at 80 ° C under an argon atmosphere.
A time reaction was performed. Thereafter, the same treatment as in Example 4 (2) was performed to obtain 1.5 g of the target polymer liquid crystal compound V.
(Mn = 16,400) The phase transition behavior of the polymer liquid crystal VI was as follows.

Electric field response speed Response time 0.3 seconds (75 ° C) Production Example 6 Polymer liquid crystal compound having a repeating unit represented by the following general formula (1) 4- (9-decenyloxy) biphenyl-4 '
Synthesis of carboxylic acid 2-methylbutyl ester 5.0 g of 10-chloro-1-decene and sodium iodide
12 g was dissolved in 50 ml of methyl ethyl ketone and stirred at 80 ° C. for 11 hours. After the reaction, the mixture was washed with water, and the organic phase was dried over magnesium sulfate. There, 4-
6.5 g of hydroxybiphenyl-4'-carboxylic acid 2-methylbutyl ester, 3.3 g of potassium carbonate and 50 ml of methyl ethyl ketone as a solvent were added, and the mixture was reacted at 80 ° C. for 28 hours. After the reaction, inorganic substances were removed by washing with water. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crude product was recrystallized from ethanol and purified to obtain the above 4- (9-decenyloxy) biphenyl-4'-carboxylic acid 2-methylbutyl ester (7.9 g, yield 81).
%).

(2) Synthesis of polymer 5.4 g of 4- (9-decenyloxy) biphenyl-4'-carboxylic acid 2-methylbutyl ester obtained in (1)
Further, 0.69 g of the polymethylhydrosiloxane used in Production Example 4 (2) was dissolved in 20 ml of toluene. 3 mg of chloroplatinic acid hexahydrate was added as a catalyst, and the mixture was heated to 80 ° C under an argon atmosphere.
For 30 hours. After that, the same operation as in Production Example 4 (2) was performed to obtain 2.0 g of the target polymer liquid crystal compound. (Mn = 16,000) The phase transition behavior of this polymer liquid crystal IV was as follows.

Electric field response speed Response time: 0.2 seconds (80 ° C) Production Example 7 (Production of polymer liquid crystal VII) Were mixed to obtain a blend type polymer liquid crystal VII.

The phase transition behavior of this polymer liquid crystal VII was as follows.

Electric field response speed Response time: 0.005 seconds (10 ° C.) Production Example 8 (Production of polymer liquid crystal VIII) Polymer liquid crystal compound having a repeating unit represented by the following general formula M. Portugall, H. Ringdorf, R. Zentel, Makromol. Chem., 1
83 , 2311 (1982), and the desired polymer liquid crystal compound VIII 1.2 g (82% yield, Mn = 7300)
I got

The phase transition behavior of the polymer liquid crystal VIII was as follows.

Production Example 9 (Production of polymer liquid crystal IX) Polymer liquid crystal compound having a repeating unit represented by the following general formula VPShibaev, SGKostromin, NAPrate, Euro.Polym.
J., 18 , 651 (1982), and synthesized the desired polymer liquid crystal compound IX 0.8 g (yield 78%, Mn8001800
0).

 The phase transition behavior of the polymer liquid crystal IX was as follows.

Production Example 10 (Production of polymer liquid crystal X) Polymer liquid crystal compound having a repeating unit represented by the following general formula Gemmell, PA, Gray, GW, Lacey, D., Mol.Cryst, Liq, Cr
The compound was synthesized according to the method described in Yst, 205 122 (1985) to obtain 2.5 g of the desired polymer liquid crystal (yield: 65%, M _n ≒ 6000).

 The phase transition behavior of the polymer liquid crystal X was as follows.

(Examples 1 to 9) Using the coating method shown in FIG. 2, under the conditions shown in Table 1, a polymer liquid crystal to be displayed was formed on a glass substrate with a transparent conductive film (ITO) which had been patterned in advance. After alignment and formation of a polymer liquid crystal coating alignment film, the same liquid crystal glass substrate with a transparent conductive film as above was sandwiched to produce a target liquid crystal optical element. About these liquid crystal optical elements,
Contrast ratio by applied voltage of display, film thickness of alignment film,
The electric field response speed was measured. The results are shown in Table 1.

(Examples 10 to 19) These examples were performed by the coating method shown in FIG.
As shown in Table 2, a polymer liquid crystal was used, and as the polymer films 7 and 8 with a conductive film, a transparent polyethylene terephthalate film using an ITO film as a transparent conductive film was coated under the conditions shown in Table 2. A liquid crystal optical element having a liquid crystal alignment film coated with a polymer liquid crystal was prepared.

With respect to these liquid crystal optical elements, the contrast ratio depending on the applied voltage for display, the thickness of the alignment film, and the electric field response speed were measured. The results are shown in Table 2.

(Examples 20 to 26) Examples 10 to 19 were performed except that the polymer liquid crystal shown in Table 3 was used and display conditions were used (however, all application rods were columnar rods). In the same manner, a liquid crystal optical element having a polymer liquid crystal coated alignment film was produced.

For these liquid crystal optical elements, the extinction ratio, the thickness of the alignment film, and the electric field response speed were measured.

 The results are shown in Table 3.

[Effects of the Invention] According to the present invention, a highly oriented polymer liquid crystal film capable of adjusting the film thickness over a wide range such as 5 μm or less and realizing improvement of electric field response and contrast is provided. By using a dielectric polymer liquid crystal, the electric field response and contrast can be further improved, and the film can be manufactured in a simple process under mild conditions such as simultaneous alignment at the same time. It is possible to provide a liquid crystal optical element which is easy and can be used as a flexible screen, and is extremely advantageous in practical use.

[Brief description of the drawings]

FIG. 1 is a sectional view showing one embodiment of a liquid crystal optical element obtained by the present invention. FIG. 2 and FIG. 3 are cross-sectional views showing examples of a film forming alignment method by a coating method in a manufacturing process of the liquid crystal optical element of the present invention. DESCRIPTION OF SYMBOLS 1 ... Polymer liquid crystal coating alignment film 2 ... Conducting film 3 ... Substrate 4 ... Fixing base with heating device 5 ... Coating rod 6 ... Polymer liquid crystal material 7 ... Height with conductive film Molecular film 8: Polymer film with conductive film 9: Coating rod, 10: Roller 11: Feeding roller 12: Roller, 13: Roller for overlapping 14: Nozzle

Claims (4)

(57) [Claims] 1. A method of manufacturing a liquid crystal optical element comprising a polymer liquid crystal film sandwiched between two transparent conductive films, at least one of which is provided with a polymer liquid crystal on the conductive film. Apply a coating rod on the polymer liquid crystal with a linear pressure of 0.5 to 1 against the polymer liquid crystal.
A method for producing a liquid crystal optical element, wherein a polymer liquid crystal film is formed by simultaneously applying and orienting by moving at a speed of 1 to 1000 mm / sec while applying a load of 00 kg / m. The load applied to the polymer liquid crystal by the movement of the coating rod is a linear pressure of 1 to 30 kg / m, and the moving speed of the coating rod is 5 to 600 mm / m.
2. The method for manufacturing a liquid crystal optical element according to claim 1, wherein the time is seconds. 3. The method for manufacturing a liquid crystal optical element according to claim 1, wherein the polymer liquid crystal is supplied onto the conductive film from a nozzle. 4. The method for producing a liquid crystal optical element according to claim 1, wherein the polymer liquid crystal is a ferroelectric polymer liquid crystal having a chiral smectic C phase.