JPH08146435A - Spacer for liquid crystal display panel, its production and liquid crystal display panel - Google Patents

Abstract

PURPOSE: To obtain the spacer for a liq. crystal display with the abnormal orientation of liq. crystal molecules at the interface between the liq. crystal and the spacer more difficult to happen by incorporating a composite grain including an org. part and an inorg. part and with the surface treated with a specified silane compd. CONSTITUTION: This spacer for a liq. crystal display panel contains an org.- inorg. composite grain including an org. part and an inorg. part, with the proportion of the inorg. part controlled to 10-90wt.%, expressed in terms of an inorg. oxide, and with the surface treated with at least one selected from among a group consisting of the silane compds. shown by formulas I and II. In the formula, X is a univalent hydrolyzable group, the four Xs can be the same or different, R<1> is a 1-20C univalent org. group having >=1 group selected from among a group consisting of amino group, hydroxyl and epoxy group, R<2> is a univalent group selected from among a group consisting of 1-20C alkyl, 6-20C aryl and 7-20C aralkyl, (m) is an integer of 1 to 3, (n) is an integer of 0 to 2, and (m+n) is an integer of 1 to 3.

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 panel, a method for manufacturing the same, and a liquid crystal display panel.

[0002]

2. Description of the Related Art A liquid crystal display (LCD) is composed of two opposing electrode substrates, a spacer and a liquid crystal material interposed between the electrode substrates. The spacer is used to keep the thickness of the liquid crystal layer uniform and constant. The display performance required for practical use of a liquid crystal display panel generally includes high-speed response, high contrast, wide viewing angle, and the like. In order to realize these various performances, it is necessary to keep the thickness of the liquid crystal layer, that is, the gap distance between the two electrode substrates strictly constant, and various spacers for liquid crystal display panels are put to practical use. There is.

Liquid crystal display panels have been manufactured by word processors, personal computers,
It has been dramatically popularized as a display device for a high-class device having a large display section or a large projection section such as a television and a projector. However, in a liquid crystal display panel using a conventional spacer, liquid crystal molecules cause abnormal alignment near the interface with the spacer. Since the area in which the abnormal orientation has occurred is not displayed, the display quality deteriorates remarkably as the area increases.

In order to suppress abnormal orientation, a silica spacer having a small surface tension (JP-A-3-293327) and a spacer obtained by treating the surface of crosslinked particles of divinylbenzene with a long-chain alkylsilane compound (JP-A-6- 1
1719) is proposed. When the spacer disclosed in the above publication is used for the liquid crystal display panel of the large-sized display section or the large-sized projection section of the above-mentioned high-grade equipment, the display area is large,
Since the number of spacers to be scattered increases and the abnormal alignment region inevitably increases or the abnormal alignment region expands, the problem of poor display quality cannot be solved.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a spacer for a liquid crystal display panel in which abnormal alignment of liquid crystal molecules at the interface between the liquid crystal and the spacer is less likely to occur. Another object of the present invention is to provide a method for easily manufacturing a spacer for a liquid crystal display panel in which abnormal alignment of liquid crystal molecules at the interface between the liquid crystal and the spacer is less likely to occur.

Still another object of the present invention is to improve the display quality of the liquid crystal display panel.

[0007]

A spacer for a liquid crystal display panel of the present invention includes an organic portion and an inorganic portion, and the proportion of the inorganic portion is 10 to 90 wt% as an inorganic oxide conversion amount.
And the surface has the general formula (1):

[0008]

[Chemical 6]

(Where X is a monovalent hydrolyzable group, and four Xs may be the same or different) and the general formula (2):

[0010]

[Chemical 7]

(Wherein R ¹ is a monovalent organic group having 1 to 20 carbon atoms and having at least one group selected from the group consisting of an amino group, a hydroxy group and an epoxy group; R
² is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted aralkyl group having 7 to 20 carbon atoms. A monovalent group selected from the group consisting of; X
Is a monovalent hydrolyzable group; m is an integer of 1 to 3; n is an integer of 0 to 2; m + n is an integer of 1 to 3; and when m is 2 or 3, Two or three R ¹ may be the same or different; when n is 2, two R ² may be the same or different; 4-m−n is 2 or 3 When 2 or 3 X may be the same or different), the organic-inorganic composite particles treated with at least one selected from the group consisting of silane compounds represented by

The method of manufacturing a spacer for a liquid crystal display panel of the present invention includes a preparation step and a surface treatment step. The preparation process is
It is a step of preparing organic-inorganic composite particles including an organic part and an inorganic part, and the ratio of the inorganic part is in the range of 10 to 90 wt% as an inorganic oxide conversion amount. In the surface treatment step, the surface of the organic-inorganic composite particles is represented by the general formula (1):

[0013]

Embedded image

(Where X is a monovalent hydrolyzable group, and four Xs may be the same or different) and the general formula (2):

[0015]

[Chemical 9]

(Wherein R ¹ is a monovalent organic group having 1 to 20 carbon atoms and having at least one group selected from the group consisting of an amino group, a hydroxy group and an epoxy group; R 1
² is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted aralkyl group having 7 to 20 carbon atoms. A monovalent group selected from the group consisting of; X
Is a monovalent hydrolyzable group; m is an integer of 1 to 3; n is an integer of 0 to 2; m + n is an integer of 1 to 3; and when m is 2 or 3, Two or three R ¹ may be the same or different; when n is 2, two R ² may be the same or different; 4-m−n is 2 or 3 And 2 or 3 Xs may be the same or different), and is treated with at least one selected from the group consisting of silane compounds represented by

In the liquid crystal display panel spacer of the present invention and the production method of the present invention, the silane compound used for the surface treatment is, for example, tetraalkoxysilane, glycidoxypropyltrialkoxysilane, or glycidoxypropylalkyldialkoxy. Silane, (epoxycycloalkyl) alkyltrialkoxysilane, aminopropyltrialkoxysilane, aminopropylalkyldialkoxysilane, N-substituted-aminopropyltrialkoxysilane, N-substituted-aminopropylalkyldialkoxysilane, hydroxypropylalkyldialkoxysilane , And at least one selected from the group consisting of hydroxypropyltrialkoxysilane.

In the spacer for a liquid crystal display panel of the present invention and the production method of the present invention, the organic-inorganic composite particles may have, for example, an organic polymer skeleton regardless of whether or not the silane compound is the above-exemplified compound. And a polysiloxane skeleton. Here, the proportion of the polysiloxane skeleton is
The amount is 25 to 85 wt% in terms of SiO _{2 with} respect to the weight of the organic-inorganic composite particles, and the polysiloxane skeleton is an organic compound in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. It has silicon in the molecule.

In the spacer for a liquid crystal display panel of the present invention and the production method of the present invention, the organic-inorganic composite particles and the organic polymer skeleton are present regardless of whether or not the silane compound is the above-exemplified compound. Whether the organic-inorganic composite particles have the general formula (3):

[0020]

[Chemical 10]

(Here, R ³ represents a hydrogen atom or a methyl group; R ⁴ represents 1 to 1 carbon atoms which may have a substituent.
10 represents an alkylene group; R ⁵ represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms).
A condensation step of hydrolyzing / polycondensing at least one hydrolyzable / condensable radically polymerizable group-containing silicon compound selected from the group consisting of compounds represented by It may be produced by a method including a polymerization step in which the radical polymerizable group is subjected to a radical polymerization reaction after the step.

In the liquid crystal display panel of the present invention, the spacer for liquid crystal display panel of the present invention is used as the spacer interposed between the electrode substrates. In the liquid crystal display panel of the present invention, the spacer for liquid crystal display panel obtained by the manufacturing method of the present invention is used as the spacer interposed between the electrode substrates.

[0023]

[Explanation of means]

[Spacer for liquid crystal display plate and method for producing the same] The particles constituting the spacer for a liquid crystal display plate of the present invention are organic-inorganic composite particles containing an organic part and an inorganic part, and the ratio of the inorganic part is the composite. 10 to 90 wt%, preferably 25 to 90% by weight in terms of inorganic oxide, based on the weight of the particles.
It is in the range of 85 wt%, more preferably 30 to 80 wt%. The inorganic oxide equivalent amount showing the ratio of the inorganic part is
It is a weight percentage obtained by measuring the weight before and after firing the organic-inorganic composite particles at a high temperature (for example, 1000 ° C.) in an oxidizing atmosphere such as air. Such composite particles are disclosed, for example, in JP-A-2-97504 2
Siloxane crosslinked polymer particles described on page 2, lower left line to page 6, lower right line 13; Japanese Patent Application No. 6-160019, page 7, line 13 to page 8, line 4, page 16 to line 14 to 14 From 3
Line, page 15, line 3 to page 18, line 3, specification 8 of Japanese Patent Application No. 6-160019.
Organic-inorganic composite particles produced by the method for producing organic-inorganic composite particles described on page 5, line 10 to page 6, line 18, line 4 to page 31, line 31, line 38, line 22 to page 47, line 13. Etc.

If the inorganic oxide equivalent amount of the organic-inorganic composite particles is less than the above range, it may be difficult to treat the surface with the silane compound and it may be difficult to suppress abnormal orientation, and if it exceeds the above range. However, it may be difficult to prevent abnormal alignment, and the film may be too hard to easily damage the alignment film or break the TFT. The most preferred organic-inorganic composite particles used in the present invention have an organic polymer skeleton and a polysiloxane skeleton having in its molecule an organic silicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. The content of the polysiloxane skeleton is in the range of 25 to 85 wt% in terms of SiO _{2 with} respect to the weight of the composite particles. The reason for this is that particles obtained by subjecting the composite particles to the surface treatment with the above-mentioned silane compound are less likely to cause damage to the alignment film and disconnection of the TFT, and the abnormal alignment is most suppressed. The SiO ₂ conversion amount indicating the ratio of the polysiloxane skeleton is 100% in the organic-inorganic composite particles in an oxidizing atmosphere such as air.
It is a weight percentage obtained by measuring the weight before and after firing at a temperature of 0 ° C. or higher.

An example of the method for producing the most preferable organic-inorganic composite particles is as follows. General formula (3):

[0026]

[Chemical 11]

(Wherein R ³ represents a hydrogen atom or a methyl group; R ⁴ represents 1 to 1 carbon atoms which may have a substituent)
10 represents an alkylene group; R ⁵ represents at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms).
While being hydrolyzed / polycondensed (during the condensation step) using at least one hydrolyzable / condensable radically polymerizable group-containing silicon compound selected from the group consisting of compounds represented by After the hydrolysis / polycondensation (after the condensation step), the radical-polymerizable group is subjected to a radical polymerization reaction (polymerization step), and in some cases, the remaining silanol groups are polycondensed (recondensation step) to obtain the most preferable organic substance. Inorganic composite particles are obtained.

Specific examples of the compound represented by the general formula (3) include, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane and γ-. Acryloxypropyltriethoxysilane, γ
-Methacryloxypropyltriacetoxysilane and the like, and any one of these may be used alone or two or more may be used in combination. As the derivative of the compound represented by the general formula (3), for example, a part of the R ⁵ O groups of the compound represented by the general formula (3) has a β-dicarbonyl group and / or another chelate compound. Selected from the group consisting of a compound substituted with a group capable of forming and a low condensation product obtained by partially hydrolyzing and polycondensing the compound represented by the general formula (3) and / or its chelate compound. Is at least one.

When the hydrolyzable / condensable radically polymerizable group-containing silicon compound is hydrolyzed / polycondensed, another hydrolyzable / condensable metal compound or silica sol may be used in combination. Specific examples of the hydrolyzable / condensable metal compound include, for example, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and ethyltrimethoxy. Organosilicon compounds such as trialkoxysilanes such as silane, and low condensation products of these tetraalkoxysilanes and / or trialkoxysilanes, and Si of these organosilicon compounds are substituted with metals such as Ti, Zr, and Al. And at least one selected from the group consisting of organic metal compounds. Examples of the silica sol include a slurry in which silica fine particles having an average particle diameter of 30 nm or less are dispersed in an organic solvent such as water and / or alcohol.

When the radical-polymerizable group is subjected to radical polymerization reaction, an organic monomer having a radical-polymerizable group and a radical-polymerizable organic group may coexist. The recondensation step is a step of accelerating the condensation of the remaining silanol groups after the completion of the above-mentioned hydrolysis / polycondensation reaction and radical polymerization reaction, and the hardness of the composite particles is improved, and the like. The number of sprays is reduced, and the display quality of the liquid crystal display panel is improved. In the recondensation step, for example, heating in an organic solvent may be performed, and in order to accelerate the condensation, as a catalyst, an organotin compound such as dibutyltin diacetate, dibutyltin silarate, dibutyltin diethyl hexanoate, or dibutyltin dimaleate is used. Etc. or acidic phosphoric acid ester may be used.

The silane compounds represented by the general formulas (1) and (2) will be described below. In the general formulas (1) and (2), X is not particularly limited as long as it is a monovalent hydrolyzable group, and for example, at least one group selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom is selected. Can be mentioned. Preferred X among the monovalent groups listed here
Is at least one group selected from the group consisting of an alkoxy group having 1 to 5 carbon atoms and an acyloxy group having 2 to 5 carbon atoms from the viewpoint that the hydrolysis by-product can be easily removed. When there are two or more X's in one molecule, they may all be the same or at least one may be different.

In the general formula (2), R ¹ is particularly limited as long as it is a monovalent organic group having 1 to 20 carbon atoms and having at least one group selected from the group consisting of an amino group, a hydroxy group and an epoxy group. Not done. Specific examples of R ¹ include, for example, γ-aminopropyl group, γ-dimethylaminopropyl group, N-β (aminoethyl) γ-aminopropyl group, N-phenyl-γ-aminopropyl group and 2-aminoethyl. Examples thereof include an aminomethyl group, a 2- (2-aminoethylthioethyl) group, a β- (3,4-epoxycyclohexyl) ethyl group, a γ-glycidoxypropyl group, and a 3-hydroxypropyl group.

In the general formula (2), R ² is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or substituted. It is not particularly limited as long as it is a monovalent group selected from the group consisting of aralkyl groups having 7 to 20 carbon atoms.
Specific examples of R ² include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, dodecyl group and octadecyl group; A group in which one or more hydrogen atoms of the alkyl group of are substituted with a halogen atom; a group in which one or more hydrogen atoms of the alkyl group having 1 to 20 carbon atoms are substituted with an alkoxy group; a phenyl group, a tolyl group, etc. An aryl group having 6 to 20 carbon atoms; a group in which one or more hydrogen atoms of these aryl groups having 6 to 20 carbon atoms are substituted with a halogen atom; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group; Examples include groups in which one or more hydrogen atoms of the aralkyl group of the formulas 7 to 20 are substituted with halogen atoms.

The silane compounds represented by the general formulas (1) and (2) are, for example, tetraalkoxysilane, glycidoxypropyltrialkoxysilane, glycidoxypropylalkyldialkoxysilane and (epoxycycloalkyl) alkyltrialkoxy. A group consisting of silane, aminopropyltrialkoxysilane, aminopropylalkyldialkoxysilane, N-substituted-aminopropyltrialkoxysilane, N-substituted-aminopropylalkyldialkoxysilane, hydroxypropylalkyldialkoxysilane, and hydroxypropyltrialkoxysilane. It is at least one selected from

Among the silane compounds represented by the general formulas (1) and (2), tetramethoxysilane, tetraethoxysilane, γ-glycidoxypropyltrimethoxysilane and γ-glyce are particularly preferable because abnormal orientation can be suppressed. Sidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane , Γ-aminopropyltriethoxysilane, γ-dimethylaminopropyltrimethoxysilane, γ-dimethylaminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ -Aminopropyltrimethoxyoxy And at least one selected from the group consisting of N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane. preferable.

As a method for treating the surface of the organic-inorganic composite particles used in the present invention with the above-mentioned silane compound, a conventionally known method is adopted and it is not particularly limited.
For example, there are the following methods. After the composite particles are immersed in the treatment liquid containing the silane compound, they are dried as they are or after filtration. A treatment liquid containing a silane compound is sprayed or applied to the composite particles and dried. The silane compound is vaporized and the gas is contacted with the composite particles.

The amount of the silane compound used is not particularly limited, but is, for example, 0.1 with respect to the weight of the composite particles.
˜500 wt%, preferably 0.5 to 100 wt%, more preferably 1 to 50 wt%. Within the range, the surface treatment effect is high, but outside the range, the surface treatment effect may be lowered. The drying temperature and time are not particularly limited. The temperature is preferably 40 to 250 ° C, more preferably 60 to 200 ° C. Time is 10 minutes ~
12 hours are preferable, and 30 minutes to 5 hours are more preferable. If the temperature or time for drying is out of the above range, the surface treatment effect may be lowered.

The spacer comprising the surface-treated particles obtained by treating the surface of the organic-inorganic composite particles with the above-mentioned silane compound is a particle in which abnormal alignment of liquid crystal molecules is suppressed. In the spacer for a liquid crystal display panel of the present invention, the particles constituting the spacer have an average particle diameter of, for example, 0.5 μm or more, preferably 0.5 to 50 μm, more preferably 1 to 25 μm, and further preferably 1.5 to 20 μm. Have.
Below the range, it is difficult to form a gap between the electrode substrates, and above the range, the region is not used as a spacer for a liquid crystal display panel. Further, the spacer for a liquid crystal display panel of the present invention is provided with, for example, a pigment and / or a pigment in order to prevent light leakage and further improve the display quality of the liquid crystal display panel.
Alternatively, particles colored with a dye may be used. Further, the spacer for a liquid crystal display panel of the present invention, for preventing the movement between the electrode substrate, to prevent damage to the alignment film and to maintain the uniformity of the gap distance to further enhance the display quality of the liquid crystal display plate, for example, The particles may be particles of a thermoplastic resin that exhibits adhesiveness when heated or coated with an adhesive layer containing the thermoplastic resin. [Liquid Crystal Display Plate] The liquid crystal display plate of the present invention is obtained by the conventional spacer for a liquid crystal display plate of the present invention and / or the production method of the present invention, instead of the conventional spacer in the conventional liquid crystal display plate. In addition, a spacer for a liquid crystal display panel is interposed between the electrode substrates.

The liquid crystal display panel of the present invention comprises, for example, a first electrode substrate, a second electrode substrate, a liquid crystal display plate spacer, a sealant and a liquid crystal. The first electrode substrate has a first substrate and a first electrode formed on the surface of the first substrate.
The second electrode substrate has a second substrate and a second electrode formed on the surface of the second substrate, and faces the first electrode substrate.
The spacer for a liquid crystal display plate is interposed between the first electrode substrate and the second electrode substrate, and is the spacer for a liquid crystal display plate of the present invention and / or the spacer for a liquid crystal display plate obtained by the manufacturing method of the present invention. Is. The sealing material bonds the first electrode substrate and the second electrode substrate at the peripheral portion. The liquid crystal is the first
The space surrounded by the electrode substrate, the second electrode substrate, and the sealing material is filled.

For the liquid crystal display panel of the present invention, those other than the spacer, such as the electrode substrate, the sealing material, and the liquid crystal, can be used in the same manner as the conventional ones. The electrode substrate has a substrate such as a glass substrate or a film substrate, and an electrode formed on the surface of the substrate. If necessary, an alignment film formed so as to cover the electrode may be further formed on the surface of the substrate. Have. An epoxy resin adhesive sealing material or the like is used as the sealing material. The liquid crystal may be one that has been conventionally used, for example, biphenyl-based, phenylcyclohexane-based, Schiff base-based, azo-based, azoxy-based,
Benzoic acid ester type, terphenyl type, cyclohexyl carboxylic acid type, biphenyl cyclohexane type,
Liquid crystals of pyrimidine type, dioxane type, cyclohexylcyclohexane ester type, cyclohexylethane type, cyclohexane type and the like can be used.

As a method for producing the liquid crystal display plate of the present invention, for example, two spacers for liquid crystal display plate of the present invention and / or two spacers for liquid crystal display plate obtained by the production method of the present invention are used as in-plane spacers. On one of the electrode substrates of 1) which is uniformly dispersed by a dry method or a wet method, the spacer for a liquid crystal display panel of the present invention and / or the spacer for a liquid crystal display panel obtained by the production method of the present invention is applied. After being dispersed in an adhesive seal material such as epoxy resin as a seal part spacer, the adhesive seal part of the other electrode substrate is coated with a means such as screen printing and placed thereon, and an appropriate pressure is applied to 100-180.
Heating at a temperature of ℃ for 1 to 60 minutes or irradiation dose of 40 to
After the adhesive sealant is heated and cured by irradiation with ultraviolet rays of 300 mJ / cm ² , liquid crystal is injected and the injection part is sealed,
A method for obtaining a liquid crystal display plate can be mentioned.

Particularly, the spacer for a liquid crystal display panel of the present invention and / or the spacer for a liquid crystal display panel obtained by the manufacturing method of the present invention suppresses the abnormal alignment of the liquid crystal and causes an abnormal alignment region near the interface between the liquid crystal molecules and the spacer. As a result, the contrast is increased and the display quality can be improved. The liquid crystal display panel of the present invention is used for the same purpose as a conventional liquid crystal display panel, and is particularly useful as an image display element for high-grade equipment such as a television, a personal computer, a word processor and a projector.

[0043]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. (Synthesis Example 1) A solution (solution A) in which a 2.9 g of 25% aqueous ammonia solution, 10.1 g of methanol and 141.1 g of water were mixed in a four-necked flask equipped with a cooling tube, a thermometer and a dropping port.
, 25 ± 2 ° C., and γ-methacryloxypropyltrimethoxysilane 3 in the solution while stirring.
2 g, 54 g of methanol, and 0.17 g of 2,2'-azobis- (2,4-dimethylvaleronitrile) as a radical polymerization initiator were added to the solution (solution B) through a dropping port to obtain γ-methacryloxypropyl. Hydrolysis and polycondensation of trimethoxysilane were performed. 2 while continuing to stir
After 0 minutes, it was heated to 70 ± 5 ° C. in an N ₂ atmosphere to carry out radical polymerization.

After continuing heating for 2 hours, cooling to room temperature,
A suspension of polymer particles was obtained. The suspension was subjected to solid-liquid separation by filtration, the obtained cake was washed 3 times by decantation with methanol, and vacuum-dried in a vacuum dryer at 200 ° C. for 2 hours to obtain composite particles (1). . The obtained composite particles (1) had an average particle diameter of 5.95 μm, a coefficient of variation of 4.2%, and a polysiloxane skeleton ratio of 24 in terms of SiO _{2 with} respect to the weight of the composite particles (1). .5 wt
%Met. Regarding the composite particles (1), a spectrum (650 to 800 cm ⁻¹ ) assigned to —CH ₂ —CH ₂ — of the organic polymer skeleton and —Si— were obtained by FT-IR analysis.
CH ₂ - spectra attributed to the (1150 to 1300
cm ^-1 ).

From these results, the composite particles (1) are
It can be seen that the organic-inorganic composite particles include an organic polymer skeleton and a polysiloxane skeleton having an organic silicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. (Example 1) 5 g of composite particles (1) obtained in Synthesis Example 1
Is dispersed in 25 g of γ-glycidoxypropyltrimethoxysilane as a silane compound, and 100 ±
Heated at 2 ° C. for 2 hours. After cooling to room temperature, it was filtered, and the obtained cake was vacuum dried at 200 ° C. to obtain surface-treated particles (1).

Next, using the surface-treated particles (1) as a spacer, a liquid crystal display panel was produced by the following method. FIG.
As shown in FIG. 1, first, after forming the electrode (for example, transparent electrode) 5 and the polyimide alignment film 4 on the lower glass substrate 111 of 300 mm × 345 mm × 1.1 mm, the lower electrode substrate is rubbed. I got 110. On the lower electrode substrate 110, the spacers (in this case, in-plane spacers) 8 for a liquid crystal display panel of the present invention were sprayed by a dry method using an electrostatic dispersion method.

On the other hand, an electrode (for example, a transparent electrode) 5 is formed on the upper glass substrate 12 of 300 mm × 345 mm × 1.1 mm.
After forming the polyimide alignment film 4 and rubbing, the upper electrode substrate 120 was obtained. The epoxy resin adhesive sealing material 112 contains 30% by volume of the liquid crystal display panel spacer (in this case, the seal portion spacer) 113 of the present invention.
What was dispersed so that it became so was screen-printed on the adhesive seal part of the upper electrode substrate 120.

Finally, the upper and lower electrode substrates 120 and 110
Are bonded via the spacer 8 of the present invention so that the electrode 5 and the alignment film 4 face each other, a pressure of 4 kg / cm ² is applied, and the adhesive sealing material 112 is heated at a temperature of 150 ° C. for 30 minutes. Heat cured. After that, the gap between the two electrode substrates 120 and 110 was evacuated and then returned to atmospheric pressure to inject the STN type liquid crystal 7 and seal the injecting portion. Then, a PVA (polyvinyl alcohol) -based polarizing film 6 was attached to the outside of the upper and lower glass substrates 12 and 111 to obtain a liquid crystal display plate.

The liquid crystal display panel using the surface-treated particles (1) as a spacer by the above-mentioned method has an abnormal alignment region of liquid crystal having a thickness of about 4% of the particle diameter around the surface-treated particles (1). Other than that, the gap distance was made uniform, the area where no image was formed was small, and the display quality was uniform. (Example 2) Surface-treated particles (2) were obtained in the same manner as in Example 1, except that the silane compound was changed to 3-hydroxypropyltrimethoxysilane.

With respect to the surface-treated particles (2), an STN type liquid crystal display panel was produced in the same manner as in Example 1. As a result, an abnormality in the liquid crystal having a thickness of about 3% of the particle diameter was observed around the surface-treated particles (2). A homogeneous display quality was obtained in the same manner as in Example 1 except that the oriented region was observed. (Example 3) Surface-treated particles (3) were obtained in the same manner as in Example 1 except that γ-aminopropyltrimethoxysilane was used instead of the silane compound.

With respect to the surface-treated particles (3), an STN type liquid crystal display panel was produced in the same manner as in Example 1. As a result, an abnormality of liquid crystal having a thickness of about 4% of the particle diameter was observed around the surface-treated particles (3). A homogeneous display quality was obtained in the same manner as in Example 1 except that the oriented region was observed. (Example 4) Surface-treated particles (4) were obtained in the same manner as in Example 1 except that the silane compound was changed to tetramethoxysilane.

When the STN type liquid crystal display panel was produced in the same manner as in Example 1 with respect to the surface-treated particles (4), an abnormal liquid crystal having a thickness of about 5% of the particle diameter was formed around the surface-treated particles (4). A homogeneous display quality was obtained in the same manner as in Example 1 except that the oriented region was observed. (Comparative Example 1) With respect to a commercially available spacer for liquid crystal display panel, Micropearl SP (crosslinked copolymer particles having an average particle diameter of 6.0 μm and containing divinylbenzene as a main component) manufactured by Sekisui Fine Chemical Co., Ltd. When an STN type liquid crystal display panel was produced in the same manner, an abnormal alignment region of the liquid crystal having a thickness of about 12% of the particle diameter was found around the spacer particles.

(Comparative Example 2) A commercially available spacer for a liquid crystal display panel, manufactured by Catalyst Kasei Co., Ltd., Masaki sphere H (average particle diameter 6.0).
When a STN type liquid crystal display plate was produced in the same manner as in Example 1 with respect to silica fine spherical particles of μm), an abnormal alignment region of liquid crystal having a thickness of about 15% of the particle diameter was found in the periphery of the spacer particles.

Comparative Example 3 Micropearl S manufactured by Sekisui Fine Chemical Co., Ltd., which is a commercially available spacer for liquid crystal display panels.
5 g of P (crosslinked copolymer particles having an average particle diameter of 6.0 μm and containing divinylbenzene as a main component, the content of an inorganic oxide when heated in an oxidizing atmosphere at 1000 ° C. 0%) is γ-glycidoxypropyl It was dispersed in 25 g of trimethoxysilane and heated at 100 ± 2 ° C. for 2 hours while stirring. After cooling to room temperature, it was filtered, and the obtained cake was vacuum dried at 200 ° C. to obtain comparative surface-treated particles (1). For the surface-treated particles for comparison (1), the STN was prepared in the same manner as in Example 1.
When a type liquid crystal display plate was produced, an abnormal alignment region of liquid crystal having a thickness of about 14% of the particle size was found around the comparative surface-treated particles (1).

(Comparative Example 4) A commercially available spacer for a liquid crystal display panel, manufactured by Catalysts & Chemicals Co., Ltd., Masaki H (average particle diameter 6.0).
5 g of silica spherical fine particles of μm, content of inorganic oxide 100% when heated in an oxidizing atmosphere at 1000 ° C.
It was dispersed in 25 g of glycidoxypropyltrimethoxysilane and heated at 100 ± 2 ° C. for 2 hours with stirring. After cooling to room temperature, it was filtered, and the obtained cake was vacuum dried at 200 ° C. to obtain comparative surface-treated particles (2). Regarding the surface-treated particles for comparison (2), S was prepared in the same manner as in Example 1.
When a TN type liquid crystal display plate was produced, an abnormal alignment region of liquid crystal having a thickness of about 16% of the particle diameter was found around the comparative surface-treated particles (1).

As can be seen from the above results, Examples 1 to 1
The abnormal orientation region of the spacer of No. 4 is reduced to about 1/4 to 1/25 in area as compared with that of the spacer of the comparative example. Therefore, the liquid crystal display panel using the spacer of the present invention, and the liquid crystal display panel of the present invention, even if it is a liquid crystal display panel of a large display section or a large projection section, has a lower display quality than the conventional one. can do.

[0057]

In the spacer for a liquid crystal display panel of the present invention, the organic-inorganic composite particles containing the organic portion and the inorganic portion in the range of 10 to 90 wt% in terms of the amount of the inorganic oxide are: Since the surface is treated with at least one selected from the group consisting of the silane compounds represented by the general formulas (1) and (2), it is possible to prevent abnormal alignment of the liquid crystal at the interface between the liquid crystal and the spacer. A liquid crystal display panel of display quality can be obtained.

The production method of the present invention comprises a preparatory step of preparing organic / inorganic composite particles containing an organic part and an inorganic part, wherein the ratio of the inorganic part is in the range of 10 to 90 wt% as an inorganic oxide equivalent amount. The surface of the organic-inorganic composite particles is at least 1 selected from the group consisting of the silane compounds represented by the general formula (1) and the general formula (2).
It is possible to prevent the abnormal alignment of the liquid crystal at the interface between the liquid crystal and the spacer, and to easily manufacture the spacer for the liquid crystal display plate that can obtain the high display quality liquid crystal display plate. it can.

In the spacer for a liquid crystal display panel of the present invention and the spacer for a liquid crystal display panel obtained by the production method of the present invention, the organic-inorganic composite particles have an organic polymer skeleton and at least one of the organic polymer skeletons. A polysiloxane skeleton having an organic silicon in which carbon atoms are directly chemically bonded to silicon atoms in the molecule, and the ratio of the polysiloxane skeleton to the weight of the composite particles is SiO ₂
When the converted amount is in the range of 25 to 85 wt%, there is an additional advantage that the number of sprayed particles can be reduced.

The liquid crystal display panel of the present invention comprises the spacer for liquid crystal display panel of the present invention and / or the spacer for liquid crystal display panel obtained by the production method of the present invention, as the spacer interposed between the electrode substrates. There is little abnormal orientation of the liquid crystal, it is easy to set the gap distance between the electrode substrates uniformly, and the reduction of the display area is small. Therefore, the liquid crystal display panel of the present invention can achieve high display quality.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view showing an example of a liquid crystal display panel of the present invention.

[Explanation of symbols]

 7 Liquid crystal 8 Spacer for liquid crystal display plate 110 Electrode substrate 113 Spacer for liquid crystal display plate 120 Electrode substrate

Claims (7)

[Claims] 1. An organic part and an inorganic part are included, and the ratio of the inorganic part is 10 to 90 wt% in terms of an inorganic oxide.
And the surface is represented by the general formula (1): (Where X is a monovalent hydrolyzable group, and four Xs may be the same or different) and the general formula (2): (Here, R ¹ is a monovalent organic group having 1 to 20 carbon atoms and having at least one group selected from the group consisting of an amino group, a hydroxy group and an epoxy group; and R ² is substituted. A monovalent alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted aralkyl group having 7 to 20 carbon atoms. X is a monovalent hydrolyzable group; m is an integer of 1 to 3; n is an integer of 0 to 2; m + n is an integer of 1 to 3; m is 2 Or 3
When two or three R ¹ may be the same or different; when n is 2, two R ¹ are
² may be the same or different; when 4-m-n is 2 or 3, 2 or 3 X's may be the same or different); A spacer for a liquid crystal display panel, which comprises organic-inorganic composite particles treated with at least one selected from the group consisting of: 2. An organic part and an inorganic part are included, and the ratio of the inorganic part is 10 to 90 wt% in terms of an inorganic oxide.
The preparation step of preparing the organic-inorganic composite particles in the range of and the surface of the organic-inorganic composite particles is represented by the general formula (1): (Where X is a monovalent hydrolyzable group, and four Xs may be the same or different) and the general formula (2): (Here, R ¹ is a monovalent organic group having 1 to 20 carbon atoms and having at least one group selected from the group consisting of an amino group, a hydroxy group and an epoxy group; and R ² is substituted. A monovalent alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and an optionally substituted aralkyl group having 7 to 20 carbon atoms. X is a monovalent hydrolyzable group; m is an integer of 1 to 3; n is an integer of 0 to 2; m + n is an integer of 1 to 3; m is 2 Or 3
When two or three R ¹ may be the same or different; when n is 2, two R ¹ are
² may be the same or different; when 4-m-n is 2 or 3, 2 or 3 X's may be the same or different); And a surface treatment step of treating with at least one selected from the following. 3. The silane compound is tetraalkoxysilane, glycidoxypropyltrialkoxysilane, glycidoxypropylalkyldialkoxysilane, (epoxycycloalkyl) alkyltrialkoxysilane, aminopropyltrialkoxysilane, aminopropylalkyl. It is at least one selected from the group consisting of dialkoxysilane, N-substituted-aminopropyltrialkoxysilane, N-substituted-aminopropylalkyldialkoxysilane, hydroxypropylalkyldialkoxysilane, and hydroxypropyltrialkoxysilane. The spacer for a liquid crystal display panel according to claim 1, or the manufacturing method according to claim 2. 4. The organic-inorganic composite particle comprises an organic polymer skeleton and a polysiloxane skeleton having in its molecule an organic silicon in which a silicon atom is directly chemically bonded to at least one carbon atom in the organic polymer skeleton. The spacer for a liquid crystal display panel according to claim 1 or 2, wherein the spacer of the polysiloxane skeleton is in the range of 25 to 85 wt% in terms of SiO _{2 with} respect to the weight of the composite particles. The manufacturing method according to claim 2 or 3. 5. The organic-inorganic composite particles have the general formula (3): (Here, R ³ represents a hydrogen atom or a methyl group; R ⁴
Represents an alkylene group having 1 to 10 carbon atoms which may have a substituent; R ⁵ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Hydrolyzing / polycondensing at least one hydrolyzable / condensable radically polymerizable group-containing silicon compound selected from the group consisting of a compound represented by the formula (1) and at least one monovalent group selected from the group 5. The liquid crystal display panel according to claim 1, 3 or 4, wherein the liquid crystal display panel is produced by a method including a condensation step of: and a polymerization step of radically polymerizing the radically polymerizable group during and / or after the condensation step. Spacer, or the manufacturing method according to claim 2, 3 or 4. 6. A liquid crystal display panel using the spacer for a liquid crystal display panel according to claim 1, as a spacer interposed between electrode substrates. 7. A liquid crystal display panel using a spacer for a liquid crystal display panel obtained by the manufacturing method according to claim 2, 3, 4, or 5 as a spacer interposed between electrode substrates.