JPH04223427A - Ferroelectric liquid crystal element - Google Patents

Abstract

PURPOSE:To provide a ferroelectric liq. crystal element consisting of a liq. crystal orienting film to obtain excellent orientation and memory characteristic at an initial stage and a liq. crystal composition to eliminate the deterioration of the characteristic with age. CONSTITUTION:Proteins are used as the material for a liq. crystal orienting film, and the rubbing directions on the upper and lower substrates are not parallel in this ferroelectric liq. crystal element. At least one kind among the compds. having a basic substituent or the epoxy compd. is added to the ferroelectric liq. crystal composition of the element. Concretely, an aliphatic primary or secondary amine is used as the compd. having a basic substituent and an epoxy compd. as the epoxy resin. Consequently, an excellent memory characteristic is secured, a uniform and even display is realized, and the excellent display is maintained for a long time.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ferroelectric liquid crystal element having a liquid crystal composition and a liquid crystal alignment film.

0002

2. Description of the Related Art In recent years, liquid crystal displays have come to be widely used not only in wristwatches, calculators, etc., but also in video equipment, and liquid crystal color televisions have also begun to appear on the market. Currently, the majority of liquid crystal panels for color display use nematic liquid crystals. However, the characteristics of nematic liquid crystals are far from ideal and include many problems. Ferroelectric liquid crystals have various properties that nematic liquid crystals do not have, such as fast response speed and memory properties, and are considered to have potential applications in display devices, and are being researched from various angles.

0003

[Problems to be Solved by the Invention] However, this ferroelectric liquid crystal cannot obtain stable memory characteristics in the initial stage. Alternatively, even if the device has stable memory characteristics and threshold characteristics initially, these characteristics deteriorate over time, resulting in a problem of poor display quality.

That is, in conventional display devices, the characteristics of the ferroelectric liquid crystal element deteriorate over time, and as a result, it is difficult to maintain good initial characteristics. In view of the above-mentioned problems with conventional liquid crystal elements, the present invention provides a liquid crystal alignment film for obtaining good initial alignment and memory properties, a liquid crystal composition for eliminating changes in properties over time, and furthermore, The purpose of the present invention is to provide a novel ferroelectric liquid crystal element by combining the following.

[0005]

A ferroelectric liquid crystal device according to claim 1 is characterized in that a protein is used as a liquid crystal alignment film material, and the rubbing directions of the upper and lower substrates are not parallel.

In the ferroelectric liquid crystal element according to claim 2, at least one compound having a basic substituent is added to the ferroelectric liquid crystal composition, a protein is used as the liquid crystal alignment film material, and the upper and lower substrates are The rubbing direction is not parallel.

[0007] The ferroelectric liquid crystal element according to claim 3 is the ferroelectric liquid crystal element according to claim 2.
The compound having a basic substituent is an amine compound. The ferroelectric liquid crystal element according to claim 4 is characterized in that in claim 2, the compound having a basic substituent is an aliphatic amine.

[0008] The ferroelectric liquid crystal element according to claim 5 is the ferroelectric liquid crystal element according to claim 2.
, the compound having a basic substituent is an aliphatic primary
Characterized by being an amine. In the ferroelectric liquid crystal device according to claim 6, in claim 5, the aliphatic primary amine is represented by the following general formula (I), in which R1 is a hydrocarbon group, and is present in the R1 group. The CH2 group is a group -O-,
It is characterized in that it may be substituted with at least one of -CO-, -OCO-, and -COO-.

(H2 N−R1 −NH2 ) ………(
I) In the ferroelectric liquid crystal device according to claim 7, in claim 5, the aliphatic primary amine is represented by the following general formula (II), in which R2 is a hydrocarbon group; It is characterized in that the CH2 groups present may be substituted by at least one of the groups -O-, -CO-, -OCO-, and -COO-.

(H2N-R2)
......(II) In the ferroelectric liquid crystal element of claim 8, in claim 2, the compound having a basic substituent is an aliphatic secondary amine represented by the following general formula (III), and in the formula: R3 is (CH2)n OH (where n is 1 or more)
, R4 is a hydrocarbon group, and the CH2 group present in the R4 group may be substituted with at least one of the groups -O-, -CO-, -OCO-, and -COO-. shall be.

[0011]The ferroelectric liquid crystal device according to claim 9 is characterized in that in claim 8, the aliphatic secondary amine is benzylethanolamine.

In the ferroelectric liquid crystal element according to claim 10, at least one type of epoxy compound is added to the ferroelectric liquid crystal composition, a protein is used as the liquid crystal alignment film material, and the rubbing direction of the upper and lower substrates is It is characterized by not being parallel.

A ferroelectric liquid crystal element according to an eleventh aspect of the present invention is characterized in that the epoxy compound is an epoxy resin. The ferroelectric liquid crystal element according to claim 12,
Claim 10 is characterized in that the epoxy compound is an epoxy compound comprising a derivative of a glycidyl group.

[0014] The ferroelectric liquid crystal element according to claim 13 is the ferroelectric liquid crystal element according to claim 10, wherein the epoxy compound is represented by the following general formula (IV).
In the formula, R5 is a hydrocarbon group, but the CH2 group present in the R5 group is a group -O-, -CO-, -O
It is characterized in that it may be substituted with at least one of CO- and -COO-.

[0015]

[Operation] The present invention improves the initial alignment state and memory property by combining the above-mentioned liquid crystal composition and liquid crystal alignment film, and the rubbing direction of the upper and lower substrates, and prevents the properties from deteriorating over time. , the lifespan of good memory characteristics can be greatly extended.

[0016]

EXAMPLE First, the physical properties of the ferroelectric liquid crystal material used in this example are shown below. Liquid crystal material: ZLI-3
654 (product name, manufactured by MERCK in Germany) Phase transition temperature: Iso 86 Ch 76 S
mA 62 SmC* However, Iso: isotropic liquid Ch: cholesteric phase SmA: smectic A phase SmC*: chiral smectic C phase Further, tilt angle: 25°, Ps: 29 nC /cm2. The phase transition temperature when 0.3% by weight of polyoxypropylene diamine (molecular weight 230) is added as the aliphatic amine is shown below.

[0017]Iso 83 Ch 73
The SmA 59 SmC* phase transition temperature was measured by texture observation using a polarizing microscope and by DSC (differential scanning calorimetry).

[0018] The structural formula of polyoxypropylene diamine (molecular weight 230) is

[0019]

[0020] Hereinafter, a liquid crystal element according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing the schematic structure of a liquid crystal element according to the present invention. A transparent electrode (ITO electrode) layer 12 made of indium tin oxide is formed on a glass or plastic substrate 11,
A coating film is formed thereon as an alignment film using a solution containing protein as a main component. Various industrially used coating methods such as spin coating, dip coating, roll coating, printing, and air knife coating can be used to form the coating film.

The protein film thus applied is subjected to an orientation treatment such as rubbing to form an orientation control film 13. At this time, alignment treatment such as rubbing is performed so that the rubbing directions on the upper and lower substrates are not parallel. Orientation control film 1 of one substrate on which orientation control film 13 is formed
A spacer/sealing resin 14 in which cylindrical or spherical spacers made of glass or plastic are dispersed in the resin is left on the side of 3 as an opening for injecting liquid crystal, and screen printing is performed. After bonding the two substrates together and curing the spacer/sealing resin 14, liquid crystal 15 is injected through the opening under reduced pressure, and the opening is sealed with a thermosetting or photocuring resin to make the ferroelectric material. Completed a liquid crystal cell.

Bovine serum albumin (BSA) as alignment film
FIG. 2 shows the threshold characteristics of a liquid crystal cell completed using the above procedure. Figures 2(a) and 2(b) show the threshold characteristics after 1000 hours when only ZLI-3654 was injected into the cell as the ferroelectric liquid crystal material, and Figure 2(c)(
d) is polyoxypropylene diamine (molecular weight 23
This figure shows the threshold characteristics after 1000 hours when a ferroelectric liquid crystal composition obtained by adding 0.3% by weight of 0) was injected into a cell. The cell gap is 2 μm. ○
The mark is the maximum relative brightness when a voltage is applied, representing the bulk response, and the cross mark is the relative brightness after scanning a series of measurement waveforms for 1000 lines, representing the memory response.

From FIG. 2, it can be seen that the threshold characteristic after 1000 hours when only the liquid crystal is injected has deteriorated, whereas the threshold characteristic of the liquid crystal added with polyoxypropylene diamine remains symmetric and steep even after 1000 hours. maintains its characteristics. This is considered to be because the polarity of the alignment film changed as a result of modification of the alignment film surface with the amine, and the interface state between the liquid crystal and the alignment film changed. Although the amount of the additive having a basic substituent is not limited, it is practically appropriate to add the additive in an amount of about 0.01 to 5% by weight. If the amount is less than the appropriate amount, the above-mentioned addition effect will not be obtained, and therefore the characteristics will deteriorate over time.

Note that the liquid crystal is not limited to ZLI-3654. Furthermore, an insulating layer may be formed on one or both sides of the transparent electrode layer 12 for the purpose of preventing short circuits between the upper and lower substrates, and the alignment control film 13 may be formed thereon.

[0025] As the protein used as the alignment film,
Various proteins can be used, including the aforementioned BSA, serum proteins such as human serum albumin, rabbit serum albumin, albumins such as ovalbumin, hemoglobin, hemotrypsin, concanavalin A, and the like.

By combining the above-mentioned protein alignment film and ferroelectric liquid crystal, a liquid crystal element with good initial alignment performance, switching performance, and memory stability can be obtained. Here, the purpose of mixing a compound having a basic substituent in the liquid crystal is to maintain the excellent initial performance thus obtained for a long period of time. At this time, the type and mixing amount of the compound having a basic substituent to be added to the liquid crystal is not specified as long as it does not impair the ferroelectricity of the liquid crystal, but specifically, benzylamine, cyclohexylamine, phenyl Compounds having basic substituents without liquid crystallinity, such as ethylamine, phenylpropylamine, benzylethanolamine, and polyoxypropylene diamine, can be used alone or in combination of two or more.

It is also effective to mix an epoxy compound into the liquid crystal instead of the above-mentioned basic compound. As the epoxy compound, epoxy compounds without liquid crystallinity such as bisphenol-type epoxy prepolymers, alicyclic epoxy prepolymers, and commercially available prepolymers can be used alone or in combination of two or more. Furthermore, an amino group or a glycidyl group may be introduced into a part of the liquid crystal molecules. [Example 1] 5.0 g of bovine serum albumin was added to 495.
It was dissolved in 0 g of pure water to prepare a 1.0% by weight bovine serum albumin aqueous solution. Next, this aqueous solution was spin-coated onto a glass substrate on which an ITO electrode pattern was formed. The coated substrate was placed in an electric furnace at 110°C and dried. When the coating film thus formed is rubbed in a single direction using a woven rayon cloth to form a liquid crystal alignment control film, the liquid crystal molecules are aligned at an angle of approximately 70° to the rubbing axis. do. Next, two glass substrates on which the bovine serum albumin orientation control film is formed are prepared, and as shown in FIG. As the sealing resin 35, an acid anhydride-curing epoxy resin in which glass fibers with a diameter of 2.0 μm are dispersed is placed in the center of only one side.
Leaving an opening 36 with a width of 0.2 mm, print with a width of 0.2 mm around the other circumference, and print a diameter of 0.2 mm on the other substrate (upper substrate 31).
The rubbing direction 33 of the alignment control film formed on the upper substrate 31 and the lower substrate 32 after spraying 2.0 μm resin spheres,
The angle formed by 34 was set to 140° so that the alignment directions of the liquid crystal molecules were parallel to each other on the upper and lower substrates, and pressure was applied with the alignment control film surfaces facing each other, and the film was heated at 140° C. for 5 hours to cure and bond. After gluing, the liquid crystal (ZL) is inserted from the opening under reduced pressure.
I3654) with polyoxypropylene diamine (molecular weight 230) as an additive having a basic substituent.
．． 3% by weight was added. After injection, the opening was sealed with a commercially available acid anhydride-curing epoxy resin. Furthermore, the encapsulated liquid crystal was heated to a temperature at which it exhibits an isotropic phase, that is, around 85° C., and the temperature was gradually lowered to complete a so-called ferroelectric liquid crystal cell.

FIG. 3 shows this ferroelectric liquid crystal cell, with 31
32 is an upper substrate, 32 is a lower substrate, 33 and 34 indicate the respective directions of rubbing treatment, and 35 is a sealing resin. The completed ferroelectric liquid crystal cell showed a good alignment state with no alignment unevenness, and when voltage was applied, good electro-optical properties with good memory properties were obtained.

[0029]Although the angle formed by the rubbing direction on the upper and lower substrates was set to 140°, the angle is not limited to this, and similar results were obtained when the angle was varied within a range of 10° before and after each. . [Example 2] 2.0g of poly-D-alanine 498
．． It was diluted with 0 g of pure water to prepare a 0.4% by weight polyalanine diluted solution. After forming polyalanine coating films on the upper and lower substrates using this solution according to the method shown in [Example 1], the coating films were rubbed so that the angle formed by the rubbing direction on the upper and lower substrates was 170°. I applied it. Thereafter, a ferroelectric liquid crystal cell was produced by the method shown in [Example 1].

However, the ferroelectric liquid crystals have the same composition (ZL
I3654) was used, but the amine was mixed with 0.3% by weight of polyoxypropylene diamine (molecular weight 230). The ferroelectric liquid crystal cell thus produced showed a good alignment state with no alignment unevenness, and upon voltage application, good electro-optic properties with memory properties ensured were obtained. This good initial performance was maintained without change even after 1000 hours when left indoors. [Example 3] 2.0 g of poly-L-alanine 498
．． It was diluted with 0 g of pure water to prepare a 0.4% by weight polyalanine diluted solution. After forming polyalanine orientation control films on the upper and lower substrates using this solution by the method shown in [Example 1], the coating films were rubbed so that the angle formed by the rubbing direction on the upper and lower substrates was 170°. was applied. Using this, a ferroelectric liquid crystal cell was produced by the method shown in [Example 1].

However, the ferroelectric liquid crystals have the same composition (ZL
I3654) was used, and 0.3% by weight of polyoxypropylene diamine (molecular weight 230) was mixed as the amine. The ferroelectric liquid crystal cell thus produced showed a good alignment state with no alignment unevenness, and upon voltage application, good electro-optic properties with memory properties ensured were obtained. This good initial performance was maintained without change even after 1000 hours when left indoors. [Example 4] 5.0 g of bovine serum albumin was added to 495.
It was diluted with 0g of pure water to prepare a 1.0% by weight bovine serum albumin diluted solution. Using this solution [Example 1]
An alignment control film of bovine serum albumin was formed by the method shown in [Example 1], and a ferroelectric liquid crystal cell was produced using this film by the method shown in [Example 1]. The same composition (ZLI3654) was used for the ferroelectric liquid crystal, but the additive was 0.
3% by weight of epoxy prepolymer (Epicote 828
: Made by Shell Kagaku Co., Ltd., Japan (trade name).

The ferroelectric liquid crystal cell produced in this manner showed a good alignment state with no alignment unevenness, and upon application of a voltage, good electro-optic properties with good memory properties were obtained. This good initial performance is 1000% when left indoors.
It remained unchanged even after hours. [Example 5] 497.5g of 2.5g of hemoglobin
of pure water to prepare a 0.5% by weight diluted hemoglobin solution. After forming a hemoglobin orientation control film using this solution by the method shown in [Example 1], the coating film was subjected to a rubbing treatment so that the angle formed by the rubbing direction between the upper and lower substrates was 170°. Thereafter, a ferroelectric liquid crystal cell was produced by the method shown in [Example 1]. The same composition (ZLI3654) was used as the ferroelectric liquid crystal, but 0.3% by weight of polyoxypropylene diamine (molecular weight 400) was mixed as an additive.

The ferroelectric liquid crystal cell thus produced showed a good alignment state with no alignment unevenness, and upon application of a voltage, good electro-optical properties with good memory properties were obtained. This good initial performance is 1000% when left indoors.
It remained unchanged even after hours. [Example 6] 2.5g of L-glutamic acid/L-lysine copolymer was diluted with 495.0g of pure water to give a concentration of 0.5% by weight.
A diluted hemoglobin solution was prepared. Using this solution, a coating film of the above copolymer was formed on each of the upper and lower substrates by the method shown in [Example 1], and then the coating film was rubbed so that the angle formed by the rubbing direction on the upper and lower substrates was 140°. Processed. Thereafter, a ferroelectric liquid crystal cell was produced by the method shown in [Example 1]. The same composition (ZLI3654) was used as the ferroelectric liquid crystal, and 0.3% by weight of polyoxypropylene diamine (molecular weight: 400) was mixed as an additive.

The ferroelectric liquid crystal cell produced in this manner showed a good alignment state with no alignment unevenness, and upon application of a voltage, good electro-optic properties with good memory properties were obtained. This good initial performance is 1000% when left indoors.
It remained unchanged even after hours. [Example 7] 1.0 g of poly-D-alanine and 1.5
g of poly-D-lysine was diluted with 497.5 g of pure to prepare a 0.5% by weight diluted solution. Using this solution, a coating film of the above mixture was formed on each of the upper and lower substrates by the method shown in [Example 1], and then the coating film was rubbed so that the angle formed by the rubbing direction on the upper and lower substrates was 170°. I applied it. After that, [Example 1]
A ferroelectric liquid crystal cell was fabricated using the method shown in . A composition (ZLI3654) was used as the ferroelectric liquid crystal, and 0.3% by weight of polyoxypropylene diamine (molecular weight 400) was mixed as an additive.

The ferroelectric liquid crystal cell produced in this manner exhibited a good alignment state with no alignment unevenness, and upon application of a voltage, good electro-optical properties with good memory properties were obtained. This good initial performance is 1000% when left indoors.
It remained unchanged even after hours.

[0036]

As described above, according to the present invention, a coating film of protein is provided on a pair of upper and lower glass substrates on which a pattern of transparent electrodes is formed in a ferroelectric liquid crystal device, and a coating film of protein is applied to the coating film on the upper and lower substrates. Good memory properties are ensured by applying a rubbing treatment so that the orientation of the molecules is parallel and using it as an alignment control film for liquid crystal, and by mixing a compound with a basic substituent into the liquid crystal composition. Moreover, it has become possible to realize a uniform and even display state, and to maintain this excellent display stably for a long period of time.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing a schematic configuration of a liquid crystal element of the present invention.

FIG. 2 is a threshold characteristic diagram after 1000 hours of a liquid crystal element of a comparative example and a threshold characteristic diagram after 1000 hours of a liquid crystal element of the present invention.

FIG. 3 is a plan view of a ferroelectric liquid crystal cell.

[Explanation of symbols]

11 Substrate 12 Transparent electrode layer 13 Orientation control film 14, 35 Spacer/seal resin 15
Liquid crystal 31 Upper substrate 32 Lower substrate 33 Rubbing direction 34 of upper substrate
Rubbing direction 36 of lower board
Aperture

Claims

[Claims] 1. A ferroelectric liquid crystal element using protein as a liquid crystal alignment film material, and in which the rubbing directions of the upper and lower substrates are not parallel. 2. A ferroelectric liquid crystal composition in which at least one compound having a basic substituent is added to a ferroelectric liquid crystal composition, a protein is used as a liquid crystal alignment film material, and the rubbing directions of the upper and lower substrates are not parallel. liquid crystal element. 3. The ferroelectric liquid crystal device according to claim 2, wherein the compound having a basic substituent is an amine compound. 4. The ferroelectric liquid crystal device according to claim 2, wherein the compound having a basic substituent is an aliphatic amine. 5. The ferroelectric liquid crystal device according to claim 2, wherein the compound having a basic substituent is an aliphatic primary amine. [Claim 6] The aliphatic primary amine is represented by the following general formula (I):
In the formula, R1 is a hydrocarbon group, but the CH2 group present in the R1 group is a group -O-, -CO-, -O
6. The ferroelectric liquid crystal element according to claim 5, which may be substituted with at least one of CO- and -COO-. (H2 N-R1 -NH2) ………(
I) [Claim 7] The aliphatic primary amine has the following general formula (
II), in which R2 is a hydrocarbon group, but R
The CH2 group present in the 2 groups is the group -O-, -CO
6. The ferroelectric liquid crystal element according to claim 5, which may be substituted with at least one of -, -OCO-, and -COO-. (H2 N-R2)
......(II) 8. The compound having a basic substituent is an aliphatic secondary compound represented by the following general formula (III).
is an amine, in the formula R3 is (CH2)nOH (however, n is 1 or more), R4 is a hydrocarbon group, but R
4 The CH2 group present in the group is the group -O-, -CO
3. The ferroelectric liquid crystal element according to claim 2, which may be substituted with at least one of -, -OCO-, and -COO-. 9. The ferroelectric liquid crystal device according to claim 8, wherein the aliphatic secondary amine is benzylethanolamine. 10. A ferroelectric liquid crystal element in which at least one type of epoxy compound is added to a ferroelectric liquid crystal composition, a protein is used as a liquid crystal alignment film material, and the rubbing directions of the upper and lower substrates are not parallel. 11. The ferroelectric liquid crystal device according to claim 10, wherein the epoxy compound is an epoxy resin. 12. The ferroelectric liquid crystal device according to claim 10, wherein the epoxy compound is an epoxy compound comprising a derivative of a glycidyl group. 13. The epoxy compound has the following general formula (I
V), in which R5 is a hydrocarbon group;
The CH2 group present in the group is the group -O-, -CO-,
11. The ferroelectric liquid crystal element according to claim 10, which may be substituted with at least one of -OCO- and -COO-.