JPH1031221A - Spacer for liquid crystal display element, liquid crystal display element, and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain spacers for a liquid crystal display element capable of preventing the abnormal orientation of liquid crystal molecules at boundary between liquid crystals and the spacer and a liquid crystal display element formed by using these spacers. SOLUTION: The spacers for the liquid crystal display element are obtd. by forming films botd. from the org. silane compd. expressed by the general formula RSX3 (where R is a 1 to 21C alkyl group, X is a halogen atom or 1 to 4C alkoxy group) on the surfaces of plastic microspheres which are microspheres obtd. by polymerizing a monomer having an ethylenic unsatd. group and consist of a monomer having >=2 pieces of ethylenic unsatd. groups (but excluding monomers consisting of an independent monomer of divinyl benzene, divinyl benzene and Y methylol alkyl Z (methacrylate) (where Y and z are integers satisfying the conditions Y>=z>=2) as a main constituting component. The spacers are formed by dispersing such spacers in an aq. dispersion medium contg, alcohol and spraying the dispersion on an electrode substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spacer for a liquid crystal display element which can prevent abnormal alignment of liquid crystal molecules,
The present invention relates to a liquid crystal display device and a method for manufacturing the same.

[0002]

2. Description of the Related Art A liquid crystal display device is generally manufactured by disposing a transparent electrode substrate on which an alignment layer is formed, facing a predetermined gap via a spacer, sealing the periphery, and injecting and sealing liquid crystal into the gap. You. The spacer is necessary to make the gap between the electrode substrates uniform.

[0003] In this type of liquid crystal display element, when abnormal alignment of liquid crystal molecules occurs in the vicinity of the spacer, a bright point or a dark point on the screen of the liquid crystal display element (these are connected to each other between the spacers, as if by a white line). May appear to be connected together, which is called a disclination line), and the display quality of the screen is degraded. In particular, this phenomenon is likely to occur in a super twisted nematic (STN) type liquid crystal display device.

At the interface between the liquid crystal molecules and the spacer,
If vertical alignment of liquid crystal molecules can be performed sufficiently,
The above bright or dark spots can be erased, so that
It is possible to dramatically improve the display quality of the liquid crystal display device.

Several methods have been proposed for preventing horizontal alignment of liquid crystal molecules at the interface between the liquid crystal molecules and the spacer and promoting vertical alignment of the liquid crystal molecules. For example, JP-A-64-59212 and JP-A-2-297523 disclose that the surface of a spacer such as glass fiber, silica, and alumina is treated with an organic silane compound (silane coupling agent) to form a liquid crystal. A method for vertically aligning molecules has been proposed.

However, the above-described conventional method is insufficient for vertically aligning liquid crystal molecules. When surface treatment of a spacer is performed with an organic silane compound to reduce abnormal alignment of liquid crystal molecules, it is extremely important to clarify the material of the spacer itself and the structure of the organic silane compound, without considering these combinations. Simply using an organic silane compound for the spacer cannot expect the effect of reducing the abnormal alignment of the liquid crystal. The conventional method leaves this point completely unknown.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to align liquid crystal molecules vertically so that abnormalities of the liquid crystal molecules at the interface between the liquid crystal and the spacer are eliminated. It is an object of the present invention to provide a spacer for a liquid crystal display element capable of preventing alignment, a liquid crystal display element, and a method for manufacturing the same.

[0008]

In order to achieve the above-mentioned object, the present invention provides a plastic microsphere obtained by polymerizing a monomer having an ethylenically unsaturated group, comprising two or more ethylenic spheres. A monomer having an unsaturated group (provided that divinylbenzene alone, divinylbenzene and Y methylolalkyl Z (meth) acrylate (where Y and Z are integers satisfying the condition of Y ≧ Z ≧ 2) Are excluded from the surface of the plastic microspheres whose main component is a general formula RSix ₃ (where R is a carbon number of 1 to 21).
Wherein X is a halogen atom or an alkoxy group having 1 to 4 carbon atoms), a spacer for a liquid crystal display element on which a coating obtained from an organic silane compound represented by the formula (1) is formed. Then, a liquid crystal display element is manufactured using the liquid crystal display element spacer.

The plastic microspheres used in the present invention are:
Plastic microspheres obtained by polymerizing a monomer having an ethylenically unsaturated group, a monomer having two or more ethylenically unsaturated groups (provided that a single monomer of divinylbenzene, divinylbenzene And Y methylolalkyl Z (meth) acrylate (where Y and Z are Y ≧ Z ≧
Excluding a monomer consisting of an integer satisfying the condition 2)).

As the monomer having two or more ethylenically unsaturated groups, the following monomers and the like are mainly used. These monomers may be used alone or in combination of two or more. However, a single monomer of divinylbenzene, divinylbenzene and Y methylolalkyl Z
(Meth) acrylate (where Y and Z are Y ≧ Z ≧ 2
Are excluded.

Y methylolalkyl Z (meth) acrylate (where Y and Z are integers satisfying the condition of Y ≧ Z ≧ 2) such as tetramethylolmethanetetra (meth) acrylate and tetramethylolmethanetri (meth) acrylate , Tetramethylolmethanedi (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate,
Glycerol di (meth) acrylate and the like can be mentioned.

The polyoxyalkylene glycol di (meth) acrylate includes, for example, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. Also, examples include triallyl (iso) cyanurate, triallyl trimellitate, and the like, divinylbenzene, diallyl phthalate, diallyl acrylamide, and the like.

These monomers are the main constituents of the plastic microspheres, and may be those containing only a monomer having two or more ethylenically unsaturated groups as a constituent. Further, a small amount of a monomer having one ethylenically unsaturated group may be used in combination with a monomer having two or more ethylenically unsaturated groups. As the monomer having one ethylenically unsaturated group, styrene-based monomers such as styrene and α-methylstyrene, and (meth) acrylates such as methyl (meth) acrylate are mainly used. These monomers may be used alone or in combination of two or more.

The plastic microspheres used in the present invention can be produced by subjecting the above-mentioned monomer having an ethylenically unsaturated group to aqueous suspension polymerization by a known method in the presence of a radical polymerization initiator. . The microspheres thus obtained preferably have a diameter in the range of 0.1 to 1000 μm, particularly preferably in the range of 1 to 100 μm. In addition,
The microspheres may be colored as needed. As the coloring agent, carbon black, disperse dye, acid dye, basic dye, metal oxide and the like are used.

The organic silane compound used in the present invention is represented by the general formula RSix ₃ (where R is an alkyl group having 1 to 21 carbon atoms, X is a chlorine atom, a bromine atom and an alkoxy group having 1 to 4 carbon atoms). ). X binds to the surface of the microspheres by hydrolysis, and those having an alkoxy group having more than 4 carbon atoms have poor reactivity and are difficult to produce industrially. In particular, X is preferably any one of a chlorine atom, a bromine atom, a methoxy group and an ethoxy group.

The alkyl group R having 1 to 21 carbon atoms promotes the liquid crystal molecules to be vertically aligned with respect to the surface of the microsphere, and those having an alkyl group having more than 21 carbon atoms are:
The effect is small because the part of the alkyl group is easy to bend,
It is also difficult to manufacture industrially. In particular, R has 2 to 1 carbon atoms.
The effect is greatest when it is a straight-chain alkyl group having no branch. .

The above-mentioned organic silane compounds include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methylmebutoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltrimethoxysilane. Butoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane,
Propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, Heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, Trialkoxylated alkylsilanes such as octadecyltriethoxysilane and the like can be mentioned.

Examples of the trihalogenated alkylsilane include methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, pentyltrichlorosilane, heptyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, nonyltrichlorosilane, decyl Trichlorosilane, dodecyltrichlorosilane, octadecyltrichlorosilane, etc., and methyltribromosilane, ethyltribromosilane, propyltribromosilane, butyltribromosilane, pentyltribromosilane, heptyltribromosilane, hexyltribromosilane, octyltri Bromosilane, nonyltribromosilane, decyltribromosilane, dodecyltribromosilane, octadecyltribromo Trihalogenated alkyl silanes such as orchids and the like.

These organic silane compounds are used alone or in combination of two or more. These organic silane compounds are used in an amount of generally 0.001 to 10 parts by weight, preferably 0.01 part by weight, based on 1 part by weight of plastic microspheres.
051 to 1 part by weight.

The spacer for a liquid crystal display element of the present invention is obtained, for example, by dissolving the above-mentioned organic silane compound in an appropriate solvent,
The plastic microspheres are immersed in the solution and heated. Thereafter, the treated plastic microspheres are collected by filtration and dried by heating to form a film of an organic silane compound on the surface of the plastic microspheres.

As the solvent for the organic silane compound, a solvent capable of dissolving the organic silane compound and having no active hydrogen that reacts with the organic silane compound is preferable. For example, aromatic solvents such as benzene, toluene, and xylene, aliphatic solvents such as hexane, heptane, octane, nonane, and decane, and alcohols and mixed solvents of alcohol and water can be used.

In particular, in the case of trialkoxylated alkylsilane, a mixed solvent of alcohol and water such as methanol, ethanol, propanol and butanol is preferable because of lower reactivity than trihalogenated alkylsilane. In this case, the mixing ratio of alcohol to water is preferably 1: 0.01 to 1: 0.5, more preferably 1: 0.05 to 1: 0.3 by weight. The amount of the solvent used for the plastic microspheres is preferably 1 to 100 parts by weight, more preferably 3 to 20 parts by weight, per 1 part by weight of the microspheres.

The heating temperature during the heating and drying is usually from 60 to 25.
0 ° C., preferably 80 to 180 ° C., and the heating time is
It is usually in the range of 30 minutes to 10 hours, preferably 1 to 3 hours.

In order to increase the adhesiveness between the plastic microspheres and the film formed on the surface thereof, and to form a relatively thin film uniformly on the surface of the microspheres, the distance between the microspheres and the film is increased. A titanium oxide layer may be provided. This titanium oxide layer can be formed using, for example, an organic titanate compound.

As the organic titanate compound, for example,
Tetraethoxytitanium, tetrapropoxytitanium, tetrobutoxytitanium, tetrapentoxytitanium, tetrahexoxytitanium, tetrakis (2-ethylhexoxy)
Titanium, tetradecoxyalkoxytitanium, tetrastearoxytitanium, dipropoxy-bis (triethanolaminato) titanium, dihydroxy-bis (lactato) titanium, titanium (acetylacetonato) titanium, dibutoxy-bis (triethanolaminato) titanium, etc. Is used.

In order to form a titanium oxide layer using an organic titanate compound, first, the organic titanate compound is dissolved in a solvent, and the obtained solution is applied to the surface of the microsphere. After that, the organic titanate compound reacts with water in the air and hydrolyzes to form a titanium oxide layer. Examples of the solvent include n-hexane, cyclohexane, benzene, toluene, trichlene, and chlorofluorocarbon (trade name).

As a method for applying the organic titanate compound to the plastic microspheres, a method in which the microspheres are immersed in a solution of the organic titanate compound and the solvent is evaporated while mixing well is preferable. After evaporating the solvent,
It is preferable to heat at 60 to 150 ° C.

The amount of titanium oxide on the surface of the plastic microspheres is preferably in the range of 0.01 to 500 mg, preferably 0.1 to 10 mg / m 2 of the surface area of the microspheres in terms of titanium.
A range of 0 mg is preferred. When the amount of titanium oxide is small, the effect of improving the adhesiveness is not so large, and when it is large, the electric resistance of the spacer is reduced.

An organic silane compound (for example, a trialkoxylated alkylsilane) is formed on the surface of the plastic microspheres.
FIG. 1 shows a schematic diagram of a reaction at the time of forming a film by the above method. First, the alkoxy group of the organic silane compound 1 is hydrolyzed to generate a substituted silanol 2.

Next, the substituted silanol 2 is condensed to form a condensate 3
To form The hydroxyl group of the condensate 3 forms a hydrogen bond 5 by hydrogen bonding with a hydroxyl group present on the surface of the plastic microspheres 4 or a hydroxyl group on the surface of the titanium oxide layer formed on the surface of the plastic microspheres 4. .

Finally, the hydrogen bond 5 is subjected to a heat treatment, whereby the hydrogen bond 5 becomes a Si—O bond and is bonded firmly to form a bond 6. In this way, a film of the organosilane compound is formed on the surface of the plastic microsphere,
The spacer for a liquid crystal display element of the present invention is manufactured.

In order to manufacture a liquid crystal display element using the spacer for a liquid crystal display element, an ordinary method is employed.
For example, as shown in FIG. 2, first, insulating films 11 (for example, SiO 2)
₂ film) is formed. Thereafter, a transparent electrode (for example, an ITO film) is formed on the insulating film 11 of each transparent substrate by patterning by photolithography.

Then, an alignment film 13 such as a polyimide film is formed on the transparent electrode 12 of each substrate. On the electrode substrate thus formed, that is, the alignment film 1 of the transparent substrate 10
The above-mentioned spacer 9 for a liquid crystal display element is sprayed on 3. The dispersion density of the liquid crystal display element spacer 9 is 50 to
200 / mm ² is preferred.

[0034] Spacer 9 for liquid crystal display element on electrode substrate
As a method of spraying, the spacer 9 for the liquid crystal display element is used.
May be sprayed as it is, but in order to spray more uniformly, it is preferable to disperse in an aqueous dispersion medium or a fluorocarbon-based dispersion medium containing an alcohol, and to spray and dry this dispersion to evaporate the dispersion medium. .

In particular, recently, regulations on chlorofluorocarbons have become strict, and an aqueous dispersion medium has been used as an alternative dispersion medium. In particular, plastic spacers tend to be difficult to disperse in the aqueous dispersion medium. is there. But,
The spacer for a liquid crystal display element of the present invention disperses well, especially in an aqueous dispersion medium containing alcohol.

Thereafter, the electrode substrates are arranged to face each other with a spacer interposed therebetween, the periphery thereof is sealed with a sealant 14, a liquid crystal 8 is injected into the gap, and the injection port is sealed to produce a liquid crystal cell. The liquid crystal display element 15 is manufactured by providing appropriate wiring to the obtained liquid crystal cell.

[0037]

The plastic microsphere used in the present invention is a plastic microsphere obtained by polymerizing a monomer having an ethylenically unsaturated group, and is a monomer having two or more ethylenically unsaturated groups. [However, a single monomer of divinylbenzene, divinylbenzene and Y methylolalkyl Z
(Meth) acrylate (where Y and Z are Y ≧ Z ≧ 2
Excluding a monomer consisting of an integer that satisfies the above condition), and the surface of the plastic microspheres has bound water and hydroxyl groups derived from the bound water because the surface of the plastic microspheres has many hydrophilic groups. There are many.

Therefore, as shown in FIG. 1, the organic silane compound is hydrolyzed by the bound water to form a substituted silanol on the surface of the plastic microspheres, and the substituted silanol reacts with the above-mentioned hydroxyl groups to form the plastic fine sphere. Easily binds to the surface of the sphere.

Therefore, a large number of alkyl groups R of the organic silane compound exist on the surface of the plastic microspheres treated with the organic silane compound. These alkyl groups R rise perpendicularly to the surface of the microsphere as a spacer. Therefore, near the surface of the spacer, as shown in FIG.
It is considered that the liquid crystal molecules are vertically aligned with respect to the surface of the spacer.

In particular, when the spacer is dispersed in an aqueous dispersion medium containing alcohol and sprayed on the electrode substrate,
The spacers are more evenly spread on the electrode substrate. The reason is that an affinity acts between the alkyl group R of the film formed on the surface of the spacer and the alkyl group of the alcohol in the aqueous dispersion medium, and as a result, the surface of the spacer was covered with alcohol molecules. State, affinity develops,
This is considered to be because it becomes easy to disperse in the aqueous dispersion medium.

[0041]

Next, the present invention will be described with reference to examples and comparative examples. (Example 1) 0.2 g of ethyltrimethoxysilane and 0.2 g of octadecyltriethoxysilane were added to hexane 10
Spacer particles (crosslinked polymer) obtained by polymerizing 70 parts by weight of diethylene glycol dimethacrylate and 30 parts by weight of divinylbenzene (average particle size: 7.82 μm, standard deviation: 0.30 μm).
g. The mixture was heated in a 45 ° C. water bath with stirring for 1 hour and then filtered. The obtained spacer particles were heated in a drier at 140 ° C. for 1 hour to obtain a spacer for a liquid crystal display element having a coating of an organic silane compound on the surface.

A pair of transparent glass substrates (300 mm ×
300 mm) on one side by SiO ₂
The film was deposited. After that, a transparent electrode film ITO was formed on the entire surface of the SiO ₂ film of one glass substrate by a sputtering method. The transparent electrode film ITO was patterned on the SiO ₂ film of the other glass substrate by ordinary photolithography.

A polyimide intermediate LP-64 (manufactured by Toray Industries, Inc.) was printed on the ITO films of both the glass substrates by an offset method, and baked at 280 ° C. for 2 hours to form a polyimide alignment film. Thereafter, when the polyimide alignment film and the liquid crystal molecules were in contact with each other, the alignment film was rubbed in a direction such that the twist angle of the liquid crystal molecules was 240 °.

After the above-mentioned spacers for liquid crystal display elements were sprayed on the electrode substrate thus obtained at a density of 120 / mm ² , seal printing was performed on the periphery of the glass substrate. A one-pack type epoxy resin (Struct Bond manufactured by Mitsui Toatsu Chemicals, Inc.) was used as a sealant.

The two electrode substrates thus prepared were stuck together so that the opposing seal printed portions were in contact with each other, and then the sealing agent was cured by heating and pressing at 180 ° C. for 1 hour. Next, the liquid crystal is injected into the gap between the cells of the electrode substrate by a conventional method, thereby
A TN liquid crystal cell was prepared.

In the liquid crystal display device using the obtained liquid crystal cell, a light spot and a dark spot (disclination line) based on the abnormal alignment of the liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element during lighting operation. Was not observed at all.
Therefore, it can be seen that the liquid crystal molecules are vertically aligned at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element.

(Example 2) Spacer particles comprising a crosslinked polymer obtained by polymerizing 70 parts by weight of diethylene glycol dimethacrylate and 30 parts by weight of divinylbenzene used in Example 1 (average particle size: 7.82 μm, standard deviation) 0.30 μm) Instead of 10 g, spacer particles composed of a crosslinked polymer obtained by polymerizing 55 parts by weight of triallyl cyanurate and 45 parts by weight of diacrylamide (average particle size: 8.25 μm, standard deviation: 0.33 μm) 10 g was used. Also, 0.2 g of ethyltrimethoxysilane and 0.2 g of octadecyltriethoxysilane used in Example 1
In place of 0.4 g of hexyltrichlorosilane was used. Other than that, it carried out similarly to Example 1.

In the liquid crystal display device using the obtained liquid crystal cell, a light spot and a dark spot (disclination line) based on the abnormal alignment of the liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element during the lighting operation. Was not observed at all.
Therefore, it can be seen that the liquid crystal molecules are vertically aligned at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element.

Comparative Example 1 In Example 1, the spacer particles composed of the crosslinked polymer were not treated with the organosilane compound. Otherwise, a spacer for a liquid crystal display element was prepared in the same manner as in Example 1 to prepare an STN liquid crystal cell.

In the liquid crystal display device using the obtained liquid crystal cell, the presence of a bright spot was confirmed during the lighting operation. Bright and dark spots (disclination lines) based on the abnormal orientation of liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element
Were observed in large numbers. Therefore, it can be seen that vertical alignment of the liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element hardly occurs.

Comparative Example 2 In Example 2, spacer particles composed of a crosslinked polymer were not treated with an organosilane compound. Otherwise, a spacer for a liquid crystal display element was prepared in the same manner as in Example 2 to prepare an STN liquid crystal cell.

In the liquid crystal display device using the obtained liquid crystal cell, the presence of a bright spot was confirmed during the lighting operation. Bright and dark spots (disclination lines) based on the abnormal orientation of liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element
Were observed in large numbers. Therefore, it can be seen that vertical alignment of the liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element hardly occurs.

Comparative Example 3 Instead of 0.2 g of ethyltrimethoxysilane and 0.2 g of octadecyltriethoxysilane used in Example 1, 0.2 g of aminopropyltriethoxysilane was used. Otherwise, a liquid crystal cell was prepared in the same manner as in Example 1.

In the liquid crystal display device using the obtained liquid crystal cell, the presence of a bright spot was confirmed during the lighting operation. Bright and dark spots (disclination lines) based on the abnormal orientation of liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element
Were observed in large numbers. Therefore, it can be seen that vertical alignment of the liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element hardly occurs.

Comparative Example 4 Spacer particles composed of a crosslinked polymer obtained by polymerizing 70 parts by weight of diethylene glycol dimethacrylate and 30 parts by weight of divinylbenzene used in Example 1 (average particle size: 7.82 μm, standard deviation) Instead of 10 g, spacer particles (average particle size: 7.90 μm, standard deviation: 0.31 μm) made of a crosslinked polymer obtained by polymerizing only divinylbenzene
g was used. Otherwise, a liquid crystal cell was prepared in the same manner as in Example 1.

In the liquid crystal display device using the obtained liquid crystal cell, the presence of a bright spot was observed at the time of lighting operation. Many dark spots (disclination lines) were observed. Therefore, it can be seen that the liquid crystal molecules are not vertically aligned at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element. This is because spacer particles consisting of a crosslinked polymer obtained by polymerizing only divinylbenzene have no hydrophilic groups on the surface,
Organic silane compounds are difficult to react, their adhesion is poor,
It is considered that a film formed by the organic silane compound was not formed well.

[0057]

As described above, when the spacer for a liquid crystal display element of the present invention is used, the liquid crystal molecules can be vertically aligned, so that the abnormal alignment of the liquid crystal molecules at the interface between the liquid crystal molecules and the spacer for the liquid crystal display element can be reduced. Can be prevented. Therefore, the liquid crystal display device using the spacer for a liquid crystal display device does not generate any bright spots and dark spots (disclination lines) at the time of lighting operation, and has excellent display quality.

In particular, when the spacer for a liquid crystal display element of the present invention is dispersed in an aqueous dispersion medium containing alcohol and sprayed on an electrode substrate, the spacer can be more uniformly formed on the electrode substrate. A liquid crystal display device having excellent display quality can be obtained. The aqueous dispersion medium is harmless as compared with the Freon-based dispersion medium, and is advantageous in manufacturing a liquid crystal display device.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a process in which a film of an organic silane compound is formed on the surface of plastic microspheres.

FIG. 2 is a sectional view of a main part of the liquid crystal display element of the present invention.

FIG. 3 is an explanatory view showing a mechanism for vertically aligning liquid crystal molecules at an interface between liquid crystal molecules and a spacer for a liquid crystal display element.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 Silane coupling agent 2 Substituted silanol 3 Condensate 4 Plastic microsphere 5 Hydrogen bond 6 Bond 7 Alkyl group of organic silane compound coating 8 Liquid crystal molecule 9 Liquid crystal display element spacer 10 Transparent substrate 11 Insulating film 12 Transparent conductive film 13 Alignment film 14 Sealant 15 Liquid crystal display element

Claims (5)

[Claims] 1. A plastic microsphere obtained by polymerizing a monomer having an ethylenically unsaturated group, comprising a monomer having two or more ethylenically unsaturated groups (provided that divinylbenzene alone is used). , A monomer comprising divinylbenzene and Y methylolalkyl Z (meth) acrylate (where Y and Z are integers satisfying the condition of Y ≧ Z ≧ 2). Obtained on the surface of the sphere from an organosilane compound represented by the general formula RSix ₃ (where R is an alkyl group having 1 to 21 carbon atoms, and X is a halogen atom or an alkoxy group having 1 to 4 carbon atoms) A spacer for a liquid crystal display element, wherein a spacer is formed. 2. Plastic microspheres obtained by polymerizing a monomer having an ethylenically unsaturated group, wherein the monomer is a monomer having two or more ethylenically unsaturated groups (provided that divinylbenzene alone is used). , A monomer comprising divinylbenzene and Y methylolalkyl Z (meth) acrylate (where Y and Z are integers satisfying the condition of Y ≧ Z ≧ 2). On the surface of the sphere, a general formula RSix ₃ (where R is a straight-chain alkyl group having 1 to 21 carbon atoms, X is any one of a chlorine atom, a bromine atom, a methoxy group and an ethoxy group) A spacer for a liquid crystal display element, wherein a coating obtained from an organic silane compound is formed. 3. A monomer having two or more ethylenically unsaturated groups is Y methylolalkyl Z (meth) acrylate (where Y and Z are integers satisfying the condition of Y ≧ Z ≧ 2), At least one of oxyalkylene glycol di (meth) acrylate, triallyl (iso) cyanurate, triallyl trimellitate, divinylbenzene, diallyl phthalate and diallyl acrylamide, provided that a single monomer of divinylbenzene, divinylbenzene and Y methylolalkyl Z (meth) acrylate (however, Y and Z are integers satisfying the condition of Y ≧ Z ≧ 2)
3. The spacer for a liquid crystal display element according to claim 1, wherein the monomer comprises: 4. A liquid crystal display device using the spacer for a liquid crystal display device according to claim 1, 2 or 3. 5. The liquid crystal display element spacer according to claim 1, 2 or 3 is dispersed in an aqueous dispersion medium containing alcohol and dispersed on an electrode substrate to form a spacer on the electrode substrate. Of manufacturing a liquid crystal display element.