JP3377978B2 - Liquid crystal display element spacer and liquid crystal display element - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display element spacer, and a liquid crystal display element using the above liquid crystal display element spacer.

[0002]

2. Description of the Related Art In general, a liquid crystal display device has a substrate on which an alignment film, a transparent electrode and the like are formed, which are opposed to each other at a predetermined interval via a spacer, and the periphery is sealed with a sealing material.
It is manufactured by injecting liquid crystal into the gap and sealing the inlet.

In this liquid crystal display element, the spacer is 2
This spacer is used to keep the distance between the substrates constant, but the spacer is required to be chemically stable in the liquid crystal, not disturb the alignment of the liquid crystal, and not move.

By the way, conventionally, in this type of liquid crystal display element, the orientation of liquid crystal molecules may be irregular at the interface between the liquid crystal and the spacer. When such an abnormal alignment occurs, when a liquid crystal display element is turned on and operated, a phenomenon called so-called light leakage through which light from the backlight is transmitted occurs. Therefore, it is known that the contrast of the liquid crystal display element is lowered and the display quality may be impaired. In particular, STN (Super Twisted Nematic)
This phenomenon was likely to occur in the liquid crystal display device of the type.

Further, the light leakage due to such an abnormal orientation is apt to occur especially when a strong impact is applied to the liquid crystal screen, and once the light leakage occurs, under normal conditions, the light leakage does not occur thereafter. Since it never disappears, it is a big problem.

Several methods for eliminating such abnormal orientation have been proposed, for example, Japanese Patent Laid-Open No. 9-113.
Japanese Patent No. 915 discloses a spacer in which a layer having an alkyl group is formed on the surface of a fine particle by treating the surface of the particle with a compound having an alkyl group in order to eliminate abnormal alignment of liquid crystals.

However, even with a spacer having a layer having an alkyl group formed on its surface, when a strong impact is applied to the liquid crystal display element, light leakage may occur from around the spacer. Then, if many spacers existing in the pixel are exposed to light, the contrast of the liquid crystal display element is significantly lowered, and the display quality is impaired.

Such light leakage violently vibrates the spacer surface and the liquid crystal when the liquid crystal display element receives an impact, and as a result, liquid crystal molecules are adsorbed on the hydrophilic portion of the spacer surface at the interface between the liquid crystal and the spacer. However, it is considered that this occurs because the orientation of the liquid crystal is different from the normal state. Therefore, there is a need for a spacer for a liquid crystal display element in which the liquid crystal around the spacer does not exhibit an abnormal orientation even when the liquid crystal display element receives a shock.

[0009]

SUMMARY OF THE INVENTION In view of the above, the present invention provides a spacer for a liquid crystal display device, which can provide a liquid crystal display device having high-quality display performance without adversely affecting the liquid crystal such as disturbing the alignment of the liquid crystal. It is also an object of the present invention to provide a liquid crystal display device using the spacer for a liquid crystal display device.

[0010]

A first aspect of the present invention is a spacer for a liquid crystal display element used in a TN (twisted nematic) type liquid crystal display element, the column being filled with the spacer for the liquid crystal display element to form a stationary phase. When a liquid crystal molecule is flowed into a system using a liquid having a solubility parameter of 8.5 to 23.5 as a mobile phase, the elution capacity of the liquid crystal molecule having an alkoxyl group is such that the alkoxyl group becomes a cyano group. The spacer for a liquid crystal display device has a larger elution capacity of liquid crystal molecules having a replaced structure. The present invention 1 will be described in detail below.
I will describe.

In the spacer for a liquid crystal display element of the present invention 1, the spacer for a liquid crystal display element is packed in a column and used as a stationary phase, and a liquid having a solubility parameter of 8.5 to 23.5 is used as a mobile phase. When liquid crystal molecules are introduced into the system, the elution capacity of liquid crystal molecules having an alkoxyl group is larger than the elution capacity of liquid crystal molecules having a structure in which an alkoxyl group is replaced with a cyano group.

When liquid crystal molecules are flowed into a column filled with spacers for a liquid crystal display element of the present invention 1 , the elution capacity of the liquid crystal molecules having an alkoxyl group is that of a liquid crystal molecule having a structure in which an alkoxyl group is replaced with a cyano group. Although the reason why the elution capacity is larger than that of the elution capacity is not clear, in the case where the hydrophobic interaction between the spacer for liquid crystal display element and the liquid crystal molecule is strong, it is considered that the alkoxyl group has stronger interaction than the cyano group. . Therefore, the present invention is applied to a liquid crystal display device.
When the liquid crystal display element spacer No. 1 is used, even if the liquid crystal display element is impacted, the alignment state of the liquid crystal does not become irregular, and the liquid crystal display element is adversely affected due to abnormal alignment such as light leakage. Does not occur.

The liquid used for the mobile phase is not particularly limited as long as it has a solubility parameter of 8.5 to 23.5, and for example, water, n-propanol, i-butanol,
Acetonitrile etc. are mentioned. The liquids having such solubility parameters may be used alone or in combination of two or more. If the solubility parameter of the liquid used for the mobile phase is less than 8.5, the hydrophobic interaction between the spacer for liquid crystal display element and the liquid crystal molecule becomes small, and the measurement becomes difficult. On the other hand, if the solubility parameter exceeds 23.5, the dispersibility of the spacer for a liquid crystal display device of the present invention in the mobile phase decreases. Incidentally, the above solubility parameter, (Delta] E ^V
/ V) ^1/2 is the amount defined. Here, ΔE ^V is the molar evaporation energy of the liquid, and V is the molar volume.

In the spacer for a liquid crystal display element of the present invention 1 ,
Since the elution capacity of liquid crystal molecules having an alkoxyl group is larger than the elution capacity of liquid crystal molecules having a structure in which an alkoxyl group is replaced with a cyano group, a structure in which the alkoxyl group is replaced with a cyano group in the elution capacity of a liquid crystal molecule having an alkoxyl group The ratio of the liquid crystal molecules to the elution capacity is greater than 1. When it is 1 or less, the performance of preventing the abnormal alignment of the liquid crystal display element spacer against impact may not be sufficient.

In the liquid crystal display element spacer of the present invention 1, when a liquid obtained by mixing n-propyl alcohol and water in a volume ratio of 1: 1 is used as a mobile phase,
The ratio of the elution capacity of liquid crystal molecules having an alkoxyl group to the elution capacity of liquid crystal molecules having a structure in which an alkoxyl group is replaced with a cyano group is preferably greater than 2.0. The above-mentioned elution capacity is the amount of liquid used for the mobile phase, which is necessary to elute the liquid crystal molecules after flowing the liquid crystal molecules into the column filled with the spacer for a liquid crystal display element of the first invention.

Examples of the spacer for a liquid crystal display device having the above-mentioned properties include those having a functional group having hydrophobic interaction with the liquid crystal introduced on the surface. The functional group exhibiting a hydrophobic interaction with the liquid crystal is not particularly limited, and examples thereof include a lauryl group, a methyl group, an ethyl group, a cetyl group, a stearyl group, a butyl group, a hexyl group, an isobutyl group, an octyl group, and a behenyl group. Alkyl groups and the like.

As a method of introducing a functional group having a hydrophobic interaction with the liquid crystal to the surface of the spacer for a liquid crystal display device, for example, a functional group having a hydrophobic interaction with the liquid crystal on the surface of the spacer having a reducing group is introduced. After being impregnated with a polymerizable monomer having, a radical is generated on the surface of the spacer by reacting with an oxidizing agent such as cerium salt or persulfate, and a graft polymerization layer is formed on the spacer surface starting from the radical. And the like.

The polymerizable monomer having a functional group exhibiting a hydrophobic interaction with the liquid crystal is not particularly limited, and examples thereof include
Lauryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, isobutyl (meth) acrylate, octyl ( Examples thereof include (meth) acrylate and behenyl (meth) acrylate. The polymerizable monomer having these functional groups is
They may be used alone or in combination of two or more.

Further, a method of introducing a polymerizable monomer having a reactive group to the surface of the spacer and then reacting the compound having a functional group having a hydrophobic interaction with the liquid crystal can be mentioned. The polymerizable monomer having a reactive group is not particularly limited, and examples thereof include a carboxyl group, a hydroxyl group, an amino group, an amide group, an epoxy group, a sulfone group, a mercapto group, a polymerization group having a reactive group such as an isocyanate group. Examples of the reactive monomer include vinyl monomers that form the above-described reactive groups by means of hydrolysis, addition, condensation, ring opening, and the like. Specifically, for example, (meth) acrylic acid, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth)
Acrylate, (meth) acrylamide, dimethylaminopropyl (meth) acrylate and the like can be mentioned. These polymerizable monomers having a reactive group may be used alone or in combination of two or more.

The compound having a functional group exhibiting a hydrophobic interaction with the liquid crystal is not particularly limited, and examples thereof include carboxylic acids, their halides and salts; alcohols; sulfonic acids, their halides and salts; amines, etc. Is mentioned. The compounds having these functional groups may be used alone or in combination of two or more. By using such a method, a functional group that exhibits a hydrophobic interaction with the liquid crystal can be introduced on the spacer surface.

The material of the spacer for liquid crystal display device of the present invention is not particularly limited, and examples thereof include epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, divinylbenzene polyester resin, divinylbenzene /
Organic substances such as styrene copolymer resin, divinylbenzene / acrylic ester resin and diacrylic phthalate resin; inorganic substances such as silicate glass, borosilicate glass, lead glass, soda lime glass, alumina and alumina silicate glass.

The shape of the spacer for a liquid crystal display device of the present invention is not particularly limited, and examples thereof include a true sphere, an elliptic sphere, and a cylinder. The particle size of the spacer for a liquid crystal display device of the present invention is 0.1 to 100 μm when the shape is a true sphere.
m is preferable, and 1 to 30 μm is more preferable.

When the shape is elliptical, the short diameter is preferably 0.1 to 100 μm, more preferably 1 to 100 μm. Furthermore, the ratio of the major diameter to the minor diameter is 1.05
10 are preferable, and 1.05-5 are more preferable.

When the shape is cylindrical, the diameter of the upper and lower bottom surfaces is preferably 0.5 to 200 μm, and 3 to 100 μm.
m is more preferred. Further, the ratio of the height of the column to the diameter is preferably 1 to 50, more preferably 1 to 10.

The present invention 2 is a spacer for a liquid crystal display element used for a TN type liquid crystal display element, wherein the spacer for a liquid crystal display element is packed in a column and used as a stationary phase, and a solubility parameter is 8.5 to 23. The following structural formula (1) was obtained when liquid crystal molecules were allowed to flow into a system using a liquid of 0.5 as the mobile phase.
The elution capacity of the liquid crystal molecules represented by is larger than the elution capacity of the liquid crystal molecules represented by the following structural formula (2).

[0026]

[Chemical 2]

In the spacer for a liquid crystal display device of the present invention 2, the spacer for a liquid crystal display device is packed in a column and used as a stationary phase, and a liquid having a solubility parameter of 8.5 to 23.5 is used as a mobile phase. When liquid crystal molecules are introduced into the system, the elution capacity of the liquid crystal molecules represented by the structural formula (1) is larger than the elution capacity of the liquid crystal molecules represented by the structural formula (2).

When liquid crystal molecules are flown into a column filled with spacers for a liquid crystal display device of the present invention 2 , the elution capacity of the liquid crystal molecules represented by the structural formula (1) is represented by the structural formula (2). The reason why the elution capacity of the liquid crystal molecule is larger than that of the liquid crystal molecule is not clear, but in the case where the hydrophobic interaction between the spacer for the liquid crystal display element and the liquid crystal molecule is strong, the liquid crystal molecule represented by the structural formula (1) has the structural formula It is considered that the interaction is stronger than that of the liquid crystal molecule represented by (2). Therefore, when the spacer for a liquid crystal display element of the present invention 2 is used for the liquid crystal display element, the alignment state of the liquid crystal does not become irregular even when the liquid crystal display element receives a shock, and the liquid crystal is caused by the alignment abnormality. The display element is not adversely affected by light leakage or the like.

In the spacer for the liquid crystal display element of the second aspect of the present invention,
Since the elution capacity of the liquid crystal molecule represented by the structural formula (1) is larger than the elution capacity of the liquid crystal molecule represented by the structural formula (2),
The ratio of the elution volume of the liquid crystal molecule represented by the structural formula (1) to the elution volume of the liquid crystal molecule represented by the structural formula (2) is 1
Get bigger. When it is 1 or less, the performance of preventing the abnormal alignment of the liquid crystal display element spacer against impact may not be sufficient.

In the spacer for a liquid crystal display element of the present invention 2, when a liquid obtained by mixing n-propyl alcohol and water in a volume ratio of 1: 1 is used as a mobile phase,
The ratio of the elution capacity of the liquid crystal molecule represented by the structural formula (1) to the elution capacity of the liquid crystal molecule represented by the structural formula (2) is
It is preferably greater than 1.5. The above-mentioned elution capacity is the amount of the liquid used for the mobile phase, which is necessary to elute the liquid crystal molecules after the liquid crystal molecules are made to flow into the column filled with the spacer for a liquid crystal display element of the present invention 2 .

A liquid having a solubility parameter of 8.5 to 23.5 in the spacer for a liquid crystal display element of the second invention is
The solubility parameter in Invention 1 is 8.5 to 23.5.
Is the same as the liquid. The other configurations of the spacer for a liquid crystal display element of the present invention 2 are the same as the configurations of the spacer for a liquid crystal display element of the present invention 1.

Since the spacers for liquid crystal display elements of the first and second aspects of the present invention have the above-mentioned structure, even if the liquid crystal display element receives an impact, the liquid crystal around the spacers is unlikely to have an abnormal orientation. Therefore, the spacers for liquid crystal display elements of the first and second aspects of the present invention can be suitably used for liquid crystal display elements. Next, the present invention 3 is the present invention 1 and the present invention 2.
A liquid crystal display element using the spacer for a liquid crystal display element. A liquid crystal display element of the present invention 3 will be described with reference to FIG.

As shown in FIG. 1, the above liquid crystal display device has a polarizing sheet 1 provided on one surface, and an insulating film 3, a transparent electrode 4 and an alignment film 5 are sequentially provided on the surface opposite to the surface provided with the polarizing sheet 1. A pair of transparent substrates 2 that are stacked and arranged so that the alignment films 5 face each other, and a liquid crystal display element spacer 7 sandwiched between the facing alignment films 5 and a liquid crystal injected between the alignment films 5. 6, and a sealing material 8 formed on the periphery.

The above liquid crystal display device can be manufactured, for example, by the following method. First, an insulating film 3 made of SiO ₂ or the like is formed on the surface of the two transparent substrates 2 provided with the polarizing sheet 1 on one surface opposite to the surface provided with the polarizing sheet 1, and then the insulating film 3 is formed. Then, the transparent electrode 4 made of ITO or the like is formed by patterning by photolithography. Thereafter, an alignment film 5 made of polyimide or the like is formed on each transparent electrode 4, and liquid crystal display element spacers 7 are scattered on the alignment film 5 of one transparent substrate 2.

After that, the substrate on which the spacers 7 for liquid crystal display elements are scattered is replaced with another substrate on which the spacers are not scattered.
The alignment films 5 are arranged so as to face each other, and an adhesive layer is formed around the substrates using a sealing material 8 to form a substrate on which liquid crystal display element spacers are dispersed and a substrate on which the spacers are not dispersed. Then, liquid crystal 6 is injected between these substrates to form a liquid crystal cell, and wiring is provided in the obtained liquid crystal cell to prepare a liquid crystal display element 10.

The spraying density when spraying the liquid crystal display element spacers on the substrate is preferably 10 to 1000 pieces / mm ² . If the dispersion density is less than 10 cells / mm ² , the gap of the liquid crystal cell may not be uniform, and the dispersion density may be 1
If it exceeds 000 pieces / mm ² , the contrast of the liquid crystal display element may decrease due to the presence of the spacer for the liquid crystal display element. Since the liquid crystal display element of the present invention 3 uses the spacer for a liquid crystal display element of the present invention, the liquid crystal around the spacer is unlikely to cause abnormal alignment even when it is impacted, and has a high quality display performance. .

[0037]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of microspheres) 800 parts by weight of a 3% aqueous solution of polyvinyl alcohol was added to
100 parts by weight of vinylbenzene, 2 parts by weight of benzoyl peroxide
Part of the mixture is added and stirred with a homogenizer to adjust the particle size.
I adjusted it. Then, while stirring, under a nitrogen stream,
The temperature was raised to 0 ° C. and the reaction was performed for 15 hours. Obtained microspheres
After washing the body with hot ion-exchanged water and methanol, classification operation
I made a work. The obtained microspheres had an average particle size of 6.0 μm,
The CV value was 5%.

(Surface Polymerization Treatment of Microspheres ) In a separable flask, the microspheres 10 produced by the above operation
0 g, ion-exchanged water 500 g, hydroxyethylmethac
300 g of relate was added and stirred. Next, select the system
A base gas was introduced, and stirring was continued at 30 ° C. for 3 hours. this
To, nitric of 0.1 mol / L was prepared in nitric acid aqueous solution of 1N
Add 200 g of ceric ammonium acid solution at 5 o'clock
Reacted for a while. After the reaction was completed, the reaction solution was taken out and the pore size was 3
Particles and reaction liquid are separated by filtration with a membrane filter of μm
did. The obtained microspheres were filled with ethanol and acetone.
It was washed for minutes and dried under reduced pressure with a vacuum dryer.

After completion of the drying, 100 g of the microspheres was added to tetrahydride.
Disperse in lofuran 1000cc, triethylamine 50
g was added. Then, under nitrogen reflux, lauryl chloride
A mixture of 50 g and 50 g of acetyl chloride was added dropwise.
Then, the mixture was reacted at 60 ° C. for 3 hours. After completion of reaction, microspheres
Dispersed in 1000 cc of methyl alcohol to give a pore size of 3 μm
The membrane filter was filtered. In addition, the microsphere is
Dispersed in 1000 cc of trahydrofuran, with a pore size of 3 μm
It was filtered with a membrane filter. This methyl alcohol
Repeat the procedure with toluene and tetrahydrofuran two more times.
After returning, it was dried under reduced pressure with a vacuum dryer to obtain surface-treated microspheres. Using the obtained microspheres as a stationary phase, the elution time of liquid crystal molecules was measured by the following evaluation method. The results are shown in Table 1 .

(Evaluation method) (Measurement of elution time) Microspheres obtained by flowing n-propanol at a constant pressure (20 MPa) into a stainless steel column having an inner diameter of 6 mm and a length of 75 mm using a liquid chromatography pump. Was packed into a column for evaluation. Further, 0.01 mol of each of the liquid crystal molecules represented by the following structural formulas (2), (3), (5) and (6) was dissolved in 1000 mL of n-propanol to obtain a measurement sample.

[0042]

[Chemical 3]

[0043]

[Chemical 4]

The obtained measurement sample was analyzed by the liquid chromatography apparatus shown in FIG. 2 under the following measurement conditions.
In the liquid chromatography device 20, the liquid feed pump 22
In the mobile phase 21 sent by the
It is automatically injected by the sampler 23. Then the measurement sample
And the mobile phase 21 was sent to the spacer packed column 24.
And then detected by the UV detector 25, recorder
A chromatogram can be obtained at 26. Got this
Calculate the elution time of the above liquid crystal molecules from the chromatogram
You can

(Measurement Conditions) (1) Mobile Phase As the mobile phase, the following five types of mobile phases (1) to (5) are used.
used. Mobile phase (1) n-propanol (solubility parameter:
11.9): water (solubility parameter: 23.4) = 1:
1 mobile phase (2) i-butanol (solubility parameter: 1
0.5): water = 1: 1 mobile phase (3) acetonitrile (solubility parameter: 1
1.9): Water = 1: 1 mobile phase (4) Methanol (solubility parameter: 14.
5): water = 1: 1 mobile phase (5) tetrahydrofuran (solubility parameter
: 9.1): Water = 1: 1 (2) Flow rate 1 mL / min (3) Column temperature 40 ° C (4) Wavelength used for UV detection 280 nm

(Production of Liquid Crystal Display Element [TN Mode]) The obtained microspheres were used as a spacer for a liquid crystal display element.
A liquid crystal display device was produced by the method below. A pair of transparent glasses
On one side of the plate (150 mm x 150 mm) by the CVD method
SiO ₂ film is vapor-deposited, and then the entire surface of the SiO ₂ film is sprayed.
An ITO film was formed by patterning. In addition, lithog
Patterning was performed by Raffy. The above pair of transparent
On the ITO film on the bright glass plate, spin coating is used to
Formed an imide intermediate (Nissan Chemical Co., SE-7210)
Then, by baking at 280 ° C for 90 minutes, polyimide
An alignment film was formed. Then, a rubbing process was performed. Then, the synthesized spacers dispersed and cloth, rubbing direction 90 °
Is opposed so that, shea Lumpur agent (HAVEN C
Both were adhered using a main agent SE4500, a curing agent T) manufactured by HEMICAL . Then, the sealing material was cured by treatment at 160 ° C. for 90 minutes to prepare an empty cell. A TN liquid crystal (MLC-6 manufactured by Merck & Co., Inc.)
After injecting 222), the injection port was closed with an adhesive to prepare a liquid crystal cell, and further heat treatment was performed at 120 ° C. for 30 minutes. Profit
For the prepared liquid crystal cell, the alignment state of the liquid crystal was evaluated as follows.
It was evaluated using the method. The results are shown in Table 1.

(Evaluation Method) (Evaluation of Alignment State) The end portion of the obtained liquid crystal cell is strongly pressed 100 times with a mallet having a rubber head.
After hitting Ku, sandwiched between the polarizing film arranged in a cross nicol state such that the normally white display mode, microscopic
Abnormality of the liquid crystal by taking a picture magnified 200 times with a mirror
The orientation (light leakage) was observed. The voltage at the time of observation is 7 volts
there were.

Example 2 The same procedure as in Example 1 was carried out except that stearyl chloride was used instead of lauryl chloride to obtain surface-treated microspheres. Using the obtained microspheres as a stationary phase, the elution time of liquid crystal molecules was measured by the same evaluation method as in Example 1 . Further, using the obtained microspheres as a spacer for a liquid crystal display element, a liquid crystal display element was produced in the same manner as in Example 1, and the alignment state of the liquid crystal was evaluated. The results are shown in Table 1 .

Example 3 (Preparation of microspheres) In the same manner as in Example 1 , microspheres were prepared. (Surface Polymerization Treatment of Microspheres) In a separable flask, the microspheres 10 produced by the above operation
0 g, ion-exchanged water 500 g, lauryl methacrylate 50 g and methyl methacrylate 200 g were added and stirred. Next, nitrogen gas was introduced into the system, and the temperature was adjusted to 3 at 30 ° C.
Stirring was continued for hours. To this, 200 g of a 0.1 mol / L ceric ammonium nitrate solution prepared with a 1N nitric acid aqueous solution was added and reacted for 5 hours. After completion of the reaction, the reaction solution was taken out and the particles and the reaction solution were separated by filtration with a membrane filter having a pore size of 3 μm. The obtained microspheres were thoroughly washed with tetrahydrofuran and acetone, and dried under reduced pressure with a vacuum dryer.

After the completion of drying, the obtained microspheres were used as a stationary phase and the elution time of liquid crystal molecules was measured by the same evaluation method as in Example 1 . Further, using the obtained microspheres as a spacer for a liquid crystal display element, a liquid crystal display element was produced in the same manner as in Example 1, and the alignment state of the liquid crystal was evaluated. Table of results
Shown in 1 .

Comparative Example 1 Microspheres were obtained in the same manner as in Example 1 except that the surface polymerization treatment was not carried out. Using the obtained microspheres as a stationary phase,
The elution time of liquid crystal molecules was measured by the same evaluation method as in Example 1 . Further, using the obtained microspheres as a spacer for a liquid crystal display element, a liquid crystal display element was produced in the same manner as in Example 1, and the alignment state of the liquid crystal was evaluated. The results are shown in Table 1 .

[0052]

[Table 1]

Table 1 shows that the elution capacity of liquid crystal molecules having an alkoxyl group is larger than the elution capacity of liquid crystal molecules having a structure in which an alkoxyl group is replaced with a cyano group.
In the liquid crystal display element using the spacers for liquid crystal display elements obtained in 1 , 2 , and 3 , there is no problem with abnormal orientation even when a shock is applied to the liquid crystal display element, or there is no problem in actual use even if there is any problem. Met. On the other hand, in the liquid crystal display device using the spacer for a liquid crystal display device of Comparative Example 1 , abnormal alignment occurred due to impact.

Example 4 The same procedure as in Example 1 was carried out to obtain surface-polymerized microspheres. Using the microspheres as a stationary phase, the elution time of liquid crystal molecules was measured by the following evaluation method. The results are shown in Table 2 .

(Evaluation method) (Measurement of elution time) Microspheres obtained by flowing n-propanol at a constant pressure (20 MPa) into a stainless steel column having an inner diameter of 6 mm and a length of 75 mm using a pump for liquid chromatography. Was packed into a column for evaluation. Further, 0.01 mol of each of the liquid crystal molecules represented by the following structural formulas (1) and (2) was dissolved in 1000 mL of n-propanol to obtain a measurement sample.

[0056]

[Chemical 5]

The obtained measurement sample was analyzed by the liquid chromatography apparatus shown in FIG. 2 under the same measurement conditions as in Example 1 to measure the elution time of liquid crystal molecules. Further, using the obtained microspheres as a spacer for a liquid crystal display element, a liquid crystal display element was produced in the same manner as in Example 1, and the alignment state of the liquid crystal was evaluated. The results are shown in Table 2 .

Example 5 The same procedure as in Example 4 was carried out except that stearyl chloride was used instead of lauryl chloride to obtain surface-treated microspheres. Using the microspheres as a stationary phase, the elution time of liquid crystal molecules was measured in the same manner as in Example 4 . Further, using the microspheres as a spacer for a liquid crystal display element, a liquid crystal display element was produced in the same manner as in Example 4, and the alignment state of liquid crystal was evaluated. The results are shown in Table 2 .

Example 6 (Preparation of Microspheres) Microspheres were prepared in the same manner as in Example 4 . (Surface Polymerization Treatment of Microspheres) In a separable flask, the microspheres 10 produced by the above operation
0 g, ion-exchanged water 500 g, lauryl methacrylate 50 g and methyl methacrylate 200 g were added and stirred. Next, nitrogen gas was introduced into the system, and the temperature was adjusted to 3 at 30 ° C.
Stirring was continued for hours. To this, 200 g of a 0.1 mol / L ceric ammonium nitrate solution prepared with a 1N nitric acid aqueous solution was added and reacted for 5 hours. After completion of the reaction, the reaction solution was taken out and the particles and the reaction solution were separated by filtration with a membrane filter having a pore size of 3 μm. The obtained microspheres were thoroughly washed with tetrahydrofuran and acetone, and dried under reduced pressure with a vacuum dryer.

After the completion of drying, the obtained microspheres were used as a stationary phase and the elution time of liquid crystal molecules was measured by the same evaluation method as in Example 4 . Further, using the obtained microspheres as a spacer for a liquid crystal display element, a liquid crystal display element was produced in the same manner as in Example 4, and the alignment state of the liquid crystal was evaluated. Table of results
Shown in 2 .

Comparative Example 2 Microspheres were obtained in the same manner as in Example 4 except that the surface polymerization treatment was not carried out. Using the obtained microspheres as a stationary phase,
The elution time of liquid crystal molecules was measured by the same evaluation method as in Example 4 . Further, using the obtained microspheres as a spacer for a liquid crystal display element, a liquid crystal display element was produced in the same manner as in Example 4, and the alignment state of the liquid crystal was evaluated. The results are shown in Table 2 .

[0062]

[Table 2]

From Table 2 , it was obtained in Examples 4 , 5 and 6 in which the elution capacity of the liquid crystal molecule represented by the structural formula (1) was larger than the elution capacity of the liquid crystal molecule represented by the structural formula (2). In the liquid crystal display element using the spacer for a liquid crystal display element, there is no problem with abnormal alignment even when a shock is applied to the liquid crystal display element, or even if there is, there is no problem in practical use. On the other hand, in the liquid crystal display device using the spacer for a liquid crystal display device of Comparative Example 2 , abnormal alignment occurred due to impact.

[0064]

Since the spacer for a liquid crystal display element of the present invention has the above-described structure, it does not adversely affect the liquid crystal such as disturbing the alignment of the liquid crystal and provides a liquid crystal display element having a high quality display performance. can do. Further, by using the spacer for a liquid crystal display element of the present invention, a liquid crystal display element having a high-quality display performance can be obtained without adversely affecting the liquid crystal such as disturbing the alignment of the liquid crystal even when a shock is applied to the liquid crystal display element. Obtainable.

[Brief description of drawings]

FIG. 1 is a cross-sectional view schematically showing a liquid crystal display element using a liquid crystal display element spacer of the present invention.

FIG. 2 is a schematic diagram of a liquid chromatography device used in Examples.

[Explanation of symbols]

1 Polarizing sheet 2 transparent substrate 3 insulating film 4 transparent electrodes 5 Alignment film 6 liquid crystal 7 Spacers for liquid crystal display elements 8 Seal material 10 Liquid crystal display element 20 Liquid chromatography 21 Mobile phase 22 Liquid feed pump 23 Auto Sampler 24 Spacer packed column 25 UV detector 26 recorder

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G02F 1/1339

Claims (5)

(57) [Claims] 1. A spacer for a liquid crystal display device used in a TN type liquid crystal display device, wherein the spacer for a liquid crystal display device is packed in a column and used as a stationary phase, and a solubility parameter is 8.5 to 23.5. When a liquid crystal molecule is introduced into a system using a liquid as a mobile phase, the elution capacity of the liquid crystal molecule having an alkoxyl group is larger than that of a liquid crystal molecule having a structure in which the alkoxyl group is replaced with a cyano group. A spacer for a liquid crystal display element, which is characterized by: 2. When a liquid in which n-propyl alcohol and water are mixed at a volume ratio of 1: 1 is used as a mobile phase, the alkoxyl group is replaced with a cyano group in the elution capacity of the liquid crystal molecule having an alkoxyl group. the ratio of the elution volume of the liquid crystal molecules with a replacement structure, the liquid crystal display element spacers according to claim 1, wherein a greater than 2.0. 3. A spacer for a liquid crystal display device used in a TN type liquid crystal display device, wherein the spacer for a liquid crystal display device is filled in a column and used as a stationary phase, and a solubility parameter is 8.5 to 23.5. When a liquid crystal molecule is introduced into a system using a liquid as a mobile phase, the elution capacity of the liquid crystal molecule represented by the following structural formula (1) is the elution capacity of the liquid crystal molecule represented by the following structural formula (2). A spacer for a liquid crystal display device, which is characterized by being larger than the capacity. [Chemical 1] 4. When a liquid in which n-propyl alcohol and water are mixed at a volume ratio of 1: 1 is used as a mobile phase, the elution capacity of liquid crystal molecules represented by the structural formula (1) The ratio of the liquid crystal molecules represented by the formula (2) to the elution capacity is
The spacer for a liquid crystal display device according to claim 3 , wherein the spacer is larger than 1.5. 5. A liquid crystal display element characterized by using a spacer for a liquid crystal display device according to claim 1, 2, 3 or 4 SL placement.