JPH11311789A - Substrate for divided alignment and liquid crystal display device using the substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to embody a good display characteristic and wide visual field angle by constituting projections formed on a substrate surface for the purpose of divided alignment of at least fillers and resin. SOLUTION: The projections are formed by preparing a paste for the projections formed by mixing and dispersing at least the fillers and the resin and applying this paste on the substrate and subjecting the coating to patterning after drying. These fillers are inorg. and org. particles having the insoluble nature to the resin forming the projections and the solvent and developer thereof. The weight ratio of the fillers and the resin is preferably 3:7 to 9:1. A black matrix 2 is formed by using a black paste on non-alkali glass 1. Blue colored layers 3 are formed so as to fill the apertures of this black matrix 2. Red colored layers 4 and green colored layers 5 are similarly formed. A transparent protective layer 6 is formed and further a transparent conductive layer 7 are laminated. The projections 8 for divided alignment are formed on the transparent conductive layer 7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a projection for split alignment and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art With the enlargement of the screen of a liquid crystal display device and its application to monitor applications, there is a demand for an increase in the viewing angle. If the tilt of the liquid crystal molecules is only one direction, the asymmetry of the viewing angle is large and the viewing angle is small in the direction in which the liquid crystal molecules are tilted. Divided orientation is a technique in which one pixel of a liquid crystal display device is divided into a plurality of regions, and the inclination of liquid crystal molecules is changed in each region.
As a division alignment technique, a technique is known in which a region in which the rubbing direction of the liquid crystal alignment film is different within one pixel using photolithography. However, productivity is reduced due to the use of photolithography having many steps. There has been a problem that the liquid crystal alignment film previously formed is damaged by a developing solution or a stripping solution used in photolithography.

On the other hand, as a liquid crystal display method, there is a vertical alignment method in which the long axis of liquid crystal molecules is oriented perpendicular to the substrate surface when no voltage is applied, and the long axis of the liquid crystal is tilted in a direction parallel to the substrate surface when voltage is applied. Proposed. Further, a technique utilizing a tilt formed on a substrate has been proposed as a vertical alignment type division alignment technique. In other words, a projection is formed on a part of the substrate, and the liquid crystal molecules that are going to align the long axis in the direction perpendicular to the substrate surface are tilted by the inclination of the side surface, and the alignment of the liquid crystal molecules in the display area is slightly shifted in the vertical direction like a shogi. It is a method of defeating from.
When a voltage is applied, the liquid crystal molecules fall further in the direction inclined by the action of the projections. If the protrusions are stripes having a triangular or trapezoidal cross section, the liquid crystal molecules are divided in two directions on two slopes and fall down, so that the liquid crystal molecules can be divided in two directions. If the projection is a pyramid, the number of alignment divisions is determined by the number of slopes. If the projection is a cone, radial liquid crystal alignment can be obtained. The slope of the side surface is a forward taper. Also,
Since the top of the projection does not contribute to display, it is desirable to be as narrow as possible. In addition, if the shape of the projections is not uniform, the liquid crystal alignment is disturbed, which causes display unevenness.
For this reason, as a method of forming the projection, photolithography capable of processing a fine pattern with high dimensional accuracy is used. That is, if the resin constituting the projection is a non-photosensitive resin, a photoresist film is formed thereon, and if the resin constituting the projection is a photosensitive resin, the resin is left alone or oxygen. After forming the blocking film, through a photomask having a predetermined pattern,
It is formed by performing exposure and development.

[0004]

However, when a projection is formed by photolithography,
When the projections are composed only of a resin, the solubility in a developing solution is remarkably large, so that it has been difficult to control the developing speed. For this reason, there has been a problem that it is difficult to stably form fine projections with high dimensional accuracy in the production process.

According to the present invention, the present inventors have studied various materials and processing methods in order to solve the above-mentioned problems. As a result, a projection formed by the following structure and a liquid crystal display device having the same have a good display. The present inventors have found that they exhibit characteristics and a wide viewing angle, and have reached the present invention.

[0006]

The object of the present invention is achieved by the following constitution.

1) A division alignment substrate used for liquid crystal display, wherein a projection formed on the substrate surface for division alignment of liquid crystal is composed of at least a filler and a resin. Substrate for alignment.

[0008] 2) The substrate according to (1), wherein the filler is at least one selected from the group consisting of barite, barium sulfate, barium carbonate, calcium carbonate, silica and talc.

3) The volume resistivity of the projection is 10 ⁷ Ωcm.
The substrate for split orientation according to (1), characterized in that:

(4) The substrate for split orientation according to (1), wherein the resin forming the protrusion is a polyimide resin or an acrylic resin.

(5) The substrate for division alignment according to any one of (1) to (4), wherein the substrate for division alignment is a color filter substrate.

(6) The substrate for split alignment according to any one of (1) to (4), wherein the substrate for split alignment is an electrode substrate.

(7) A liquid crystal display device using the substrate for divisional alignment according to any one of (1) to (6).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The projections of the present invention are prepared by first preparing a projection paste obtained by mixing and dispersing at least a filler and a resin constituting the projections, applying the paste on a substrate and drying the paste. It is formed by performing.

In the present invention, the filler constituting the projection refers to a resin constituting the projection, and inorganic and organic particles having a property of being insoluble in a solvent and a developing solution thereof. As inorganic particles, silica, barium sulfate, barium carbonate, calcium carbonate, extender pigments such as talc,
And black, red, blue, green and other coloring pigments, and alumina,
Ceramic powders such as zirconia, magnesia, beryllia, mullite, cordierite, and glass-ceramic composite powders are used. Of the extender pigments, barite, barium sulfate, barium carbonate, calcium carbonate, silica and talc are particularly preferred because they have no coloring and can make the projections transparent. When projections are required to be light-shielding, carbon black, titanium black (TiNxO
y: However, 0 ≦ x <1.5, 0.1 <y <1.8),
Metal oxide powder such as manganese oxide and iron tetroxide, metal sulfide powder, and metal powder can be used. Among them, carbon black is excellent in light-shielding properties and is particularly preferable.
When the projections are required to have a light-shielding property and an insulating property, insulating inorganic particles such as aluminum oxide, titanium black, and iron oxide, or carbon black having a surface coated with a resin may be used.

As the organic particles, resin beads polymerized with a high molecular weight or a high degree of crosslinking are preferably used.

The average primary particle diameter of the filler is 5-4.
The thickness is preferably 0 nm, more preferably 6 to 35 nm, and still more preferably 8 to 30 nm.

In some cases, the filler aggregates in the projection paste to form secondary particles of the filler. When the average of these particle diameters is defined as the average secondary particle diameter, the filler is finely reduced so that the average secondary particle diameter becomes small. It is preferable to disperse, and it is more preferable to disperse the primary particles with good stability without forming secondary particles. The average secondary particle diameter is preferably from 5 to 100 nm, more preferably from 6 to 88 nm, and still more preferably from 8 to 75 nm. If it is larger than this, projections and depressions are formed on the surface of the projection, and display defects are caused due to disorder of liquid crystal alignment, which is not preferable. The average primary particle diameter and the average secondary particle diameter are determined, for example, by observing the filler with a transmission or scanning electron microscope or the like, and determining the average particle diameter according to JIS-R6002.

In the present invention, the resin constituting the projection is preferably a photosensitive or non-photosensitive resin such as a polyimide resin, an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, and a polyolefin resin. They are used, but are not limited to these as long as they do not have the property of dissolving the filler constituting the projections.

As the photosensitive resin, there are types such as a photodecomposable resin, a photocrosslinkable resin, and a photopolymerizable resin.
A photosensitive composition, a photosensitive polyamic acid composition, or the like containing a monomer, oligomer, or polymer having an ethylenically unsaturated bond and an initiator that generates a radical by ultraviolet light is preferably used.

As the non-photosensitive resin, those which can be developed with the above-mentioned various polymers are preferably used. However, the non-photosensitive resin should be able to withstand the heat in the process of forming a transparent conductive layer and the process of manufacturing a liquid crystal display device. A resin having excellent heat resistance is preferable, and a resin having resistance to an organic solvent used in a manufacturing process of a liquid crystal display device is preferable, and a polyimide resin is particularly preferable.

Here, the polyimide resin is not particularly limited, but usually a polyimide precursor having a structural unit represented by the following general formula as a main component is imidized by heating or an appropriate catalyst. Are preferably used.

[0023]

Embedded image Here, n in the above general formula is 0 or a number of 1 to 4.
R ¹ is an acid component residue, and R ¹ is a trivalent or tetravalent organic group having at least two carbon atoms. From the viewpoint of heat resistance, R ¹ is preferably a trivalent or tetravalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Examples of R ¹ include a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group,
Examples include, but are not limited to, groups derived from a diphenyl ether group, a diphenylsulfone group, a diphenylpropane group, a benzophenone group, a biphenyltrifluoropropane group, a cyclobutyl group, a cyclopentyl group, and the like.

R ² represents a divalent organic group having at least two carbon atoms. From the viewpoint of heat resistance, R ² is preferably a divalent group containing a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Examples of R ² include phenyl, biphenyl, terphenyl, naphthalene, perylene, diphenylether, diphenylsulfone, diphenylpropane, benzophenone, biphenyltrifluoropropane, diphenylmethane, cyclohexylmethane, and the like. Derived groups include, but are not limited to.
In the polymer having the structural unit represented by the general formula (1) as a main component, R ¹ and R ² may each be composed of one of these, or a copolymer composed of two or more of each. It may be.

The weight ratio of the filler to the resin is 3: 7 to 9:
1, more preferably 4: 6 to 8:
2. If the weight ratio of the filler is too small, the developing speed at the time of patterning the projections increases, and it becomes difficult to obtain a desired projection shape. On the other hand, if the weight ratio of the filler is too large, aggregation of the filler occurs or it becomes difficult to adjust the paste for projection to a desired viscosity, which is not preferable.

Further, it is preferable that the weight ratio of the filler to the resin is within the above range in that the elastic modulus of the projection is improved and the projection has strength. If the strength of the projection is low, deformation occurs, causing display unevenness due to poor alignment of the liquid crystal.

In the projection paste of the present invention, as a method of dispersing the filler in the resin, a method in which the resin and the filler are mixed in a solvent and then dispersed in a disperser such as a three-roll mill, a side grinder, and a ball mill. Etc., but is not particularly limited to this method.

Further, various additives may be added for improving the dispersibility of the filler, or for improving the coating property and leveling property.

As a method of forming the projections of the present invention on the color filter and on the electrode substrate facing the color filter, first, a projection paste is applied on the substrate, dried,
Perform patterning. As a method of applying the paste for projection, a dip method, a roll coater method, a spinner method,
A die coating method, a wire bar coating method, or the like is suitably used, and thereafter, heat drying (semi-curing) is performed using an oven or a hot plate. The semi-curing conditions vary depending on the resin, solvent and paste applied amount, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.

When the resin is a non-photosensitive resin, the paste film for projections obtained as described above is formed after a photoresist film is formed thereon, or when the resin is a photosensitive resin. Is exposed or developed as it is or after forming an oxygen barrier film. If necessary, the photoresist film or the oxygen blocking film is removed, and the film is dried by heating (this cure). These curing conditions are slightly different depending on the coating amount when a polyimide resin is obtained from the precursor, but it is generally heated at 200 to 300 ° C. for 1 to 60 minutes. In the case of an acrylic resin, the curing condition is generally to heat at 150 to 300 ° C. for 1 to 60 minutes. Through the above process, projections are formed on the substrate surface. When it is difficult to obtain a sufficient height by one patterning, a plurality of paste layers for projections can be stacked.

The projections may be formed by a transfer method. In other words, a transfer substrate having a paste layer for projections formed on a substrate in advance is prepared, and the transfer substrate is overlaid on the substrate while applying heat and pressure as necessary, exposed and developed, and then the substrate is peeled. In this method, the projections are formed on the transfer substrate by photolithography, and then the projections are transferred onto the substrate by applying heat or pressure.

The height of the projection of the present invention is 0.5 μm to 6 μm.
It is preferred that If the projection height is less than 0.5 μm, the effect of the split orientation is not sufficient, while the projection height is 6 μm.
If it exceeds μm, it becomes difficult to form projections by one photolithography, and it also hinders liquid crystal injection. The height of the split alignment projection is more preferably in the range of 0.6 μm to 3 μm.

The projections need to be paired with the color filter side and the opposing electrode substrate. Therefore, the cross sections are trapezoidal or triangular stripes, and are alternately arranged on the color filter side and the opposing electrode substrate. Is particularly preferred.

The protrusion of the present invention has a volume resistivity of 10 ⁷ Ωcm.
It is preferable that it is above. The volume resistance of the projection is 10 ⁷
If it is less than Ωcm, a sufficient voltage is not applied to the liquid crystal, which causes display failure, which is not preferable. More preferably, the volume resistance value is 10 ⁹ Ωcm or more.

The projection of the present invention is required to have high heat resistance and solvent resistance since a liquid crystal alignment film is formed thereon.
In addition, since the liquid crystal and the protrusion are adjacent to each other via a thin liquid crystal alignment film having a thickness of 0.1 μm or less, elution of ionic impurities is small and excellent electric characteristics are required. As the resin constituting the projection of the present invention, a polyimide resin or an acrylic resin satisfying the above conditions is preferable.

Hereinafter, the present invention will be described in more detail.

The color filter of the present invention is preferably one in which a black matrix is provided on a transparent substrate as required, and a plurality of colored layers of three primary colors are further arranged thereon. The color filter is composed of a large number of picture elements, with a pixel covered by each colored layer of three primary colors as one picture element. Here, the black matrix indicates a light-shielding region arranged between each pixel, is provided to improve display contrast of a liquid crystal display device, and to prevent light from entering an active element such as a TFT and causing a malfunction. .

The transparent substrate used for the color filter is not particularly limited, and inorganic glass such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass whose surface is coated with silica, etc.
Organic plastic films or sheets are preferably used.

A black matrix is provided on the transparent substrate as needed. The black matrix may be formed by overcoating a metal such as chromium or nickel or their oxides, or a colored layer, but forming a resin black matrix composed of a resin and a light-shielding agent requires manufacturing costs and waste treatment. It is preferable from the viewpoint of cost. In this case, the resin used for the black matrix is not particularly limited, but an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin,
A photosensitive or non-photosensitive material such as a polyolefin resin is preferably used. The resin for the black matrix is preferably a resin having higher heat resistance than the resin used for the pixels and the protective film, and a polyimide resin is preferably a resin having resistance to the organic solvent used in the process after the formation of the black matrix. Resins are particularly preferably used. In addition, as a preferable polyimide-based resin, a resin suitable for forming the above-mentioned protrusion can be used.

As the light shielding agent for the black matrix, carbon black, titanium black (TiNxO)
y: However, 0 ≦ x <1.5, 0.1 <y <1.8),
In addition to metal oxide powders such as manganese oxide and iron tetroxide, metal sulfide powders, and metal powders, a mixture of pigments such as red, blue, and green can be used. Among them, carbon black is particularly preferable because of its excellent light-shielding properties. Since carbon black having a good dispersion and a small particle size mainly exhibits a brownish color tone, it is preferable to mix a pigment of a complementary color to carbon black to obtain an achromatic color.

When the resin for the black matrix is polyimide, the black paste solvent is usually N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Amide polar solvents such as N, N-dimethylformamide,
A lactone polar solvent such as γ-butyrolactone is preferably used.

As a method of dispersing a light-shielding agent such as a pigment of a complementary color to carbon black or carbon black, for example, after mixing a light-shielding agent or a dispersant in a polyimide precursor solution, a three-roll Sand grinder,
There is a method of dispersing in a dispersing machine such as a ball mill, but the method is not particularly limited. In addition, various additives may be added for improving the dispersibility of carbon black, or for improving applicability and leveling property.

As a method for producing a resin black matrix, a black paste is applied to a transparent substrate, dried,
Perform patterning. As a method for applying the black paste, a dip method, a roll coater method, a spinner method, a die coating method, a wire bar coating method, or the like is suitably used. After that, heat drying (semi-curing) using an oven or a hot plate is performed. Do. The semi-curing conditions vary depending on the resin, solvent and paste applied amount, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.

The black paste film obtained in this manner is formed after forming a photoresist film thereon when the resin is a non-photosensitive resin, and when the resin is a photosensitive resin when the resin is a non-photosensitive resin. Exposure and development are performed as it is or after forming an oxygen barrier film. If necessary, the photoresist film or the oxygen barrier film is removed, and the film is dried by heating (this cure). These curing conditions are slightly different depending on the coating amount when a polyimide resin is obtained from the precursor, but it is generally heated at 200 to 300 ° C. for 1 to 60 minutes. In the case of an acrylic resin, the curing condition is generally to heat at 150 to 300 ° C. for 1 to 60 minutes. Through the above process, a black matrix is formed on the substrate.

The resin black matrix may be formed by a transfer method. A black matrix may be formed by stacking colored layers described later.

The thickness of the resin black matrix is preferably 0.5 to 2.0 μm, more preferably 0.8 to 1.
5 μm. When the film thickness is smaller than 0.5 μm, it is difficult to form a spacer having a sufficient height when forming a spacer by laminating a resin layer on a resin black matrix. It is not preferable because it becomes insufficient. On the other hand, when the film thickness is greater than 2.0 μm, although the light-shielding property can be ensured, the flatness of the color filter is easily sacrificed, and a step is easily generated.

The light shielding property of the resin black matrix is O
It is represented by the D value (common logarithm of the reciprocal of the transmittance), and is preferably 1.6 or more, more preferably 2.0 or more, in order to improve the display quality of the liquid crystal display device.
The preferred range of the thickness of the resin black matrix has been described above, but the upper limit of the OD value should be determined in relation to this.

Usually, (2)
An opening of 0 to 200) μm × (20 to 300) μm is provided.
A plurality of primary color layers are arranged. That is,
One opening is covered with any one of the three primary color layers, and a plurality of color layers of each color are arranged.

In the case of a color filter, the coloring layer comprises at least three primary colors, red (R), green (G), blue (B) or
It includes three layers of cyan (C), magenta (M), and yellow (Y), and each pixel is provided with one colored layer of any of these three colors.

As the coloring agent used in the coloring layer, organic pigments, inorganic pigments, dyes and the like can be preferably used. Further, various additives such as an ultraviolet absorber, a dispersing agent and a leveling agent are added. You may. As the pigment, Color Index Nos. 9, 97, 122, 123, and 14 as red (R)
9, 168, 177, 180, 192, 215, etc. Color Index No. 7, 36 as blue (G) Blue (B) as green (G)
Color Index Nos. 15, 22, 60, 64, etc. are generally used. A wide range of dispersants such as surfactants, pigment intermediates, dye intermediates, and polymer dispersants are used.

The resin used for the colored layer is not particularly limited, but may be an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin,
A photosensitive or non-photosensitive material such as a polyolefin resin can be employed.

As a method of forming a colored layer, a paste containing a colorant is applied to a substrate on which a black matrix is formed, dried, and then patterned. As a method of obtaining a colored paste by dispersing or dissolving the colorant, after mixing the resin and the colorant in a solvent, three-roll, sand grinder, there is a method of dispersing in a dispersing machine such as a ball mill, The method is not particularly limited.

As a method of applying the colored paste, a dipping method, a roll coater method, a spinner method, a die coating method, a wire bar coating method, etc. are preferably used, as in the case of the black paste, and thereafter, an oven or hot Heat drying (semi-cure) is performed using a plate. The semi-curing conditions vary depending on the resin used, the solvent, and the amount of the paste applied, but it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.

In the colored paste film thus obtained, after a photoresist film is formed thereon when the resin is a non-photosensitive resin, and when the resin is a photosensitive resin, Exposure and development are performed as it is or after forming an oxygen barrier film. If necessary, the photoresist film or the oxygen barrier film is removed, and the film is dried by heating (this cure).

The curing conditions are slightly different depending on the coating amount when a polyimide resin is obtained from the precursor, but it is generally heated at 200 to 300 ° C. for 1 to 60 minutes. In the case of an acrylic resin, the curing condition is generally to heat at 150 to 300 ° C. for 1 to 60 minutes. Through the above process, a patterned colored layer is formed on the substrate on which the black matrix is formed. Further, the colored layer may be formed by a so-called transfer method.

Further, in the color filter of the present invention, a transparent protective layer may be formed before forming the transparent conductive layer. The formation of such a transparent protective layer is disadvantageous in that the structure of the color filter is complicated and the production cost is increased, but on the other hand, it is necessary to control the height of the spacer, to prevent impurities from being stained from the color filter, and to planarize the surface. It is advantageous.

After the formation of the three colored layers or the formation of the transparent protective layer, a transparent conductive layer is formed. An oxide thin film such as ITO can be used as the transparent conductive layer.

After the color filter is manufactured by the above-described process, the projection for split alignment of the present invention is formed.

The method of manufacturing a color filter of the present invention and a liquid crystal display device using the same will be described below with reference to FIGS. 1 and 2, but the present invention is not limited thereto.

A black matrix 2 is formed on a non-alkali glass 1 using a black paste. Next, a blue coloring layer 3 is formed so as to fill the opening of the black matrix. Similarly, a red coloring layer 4 and a green coloring layer 5 are formed. Next, a transparent protective layer 6 is formed, and a transparent conductive layer 7 is further laminated. The projections 8 for divisional alignment are formed on the transparent conductive layer.

An example of a method for manufacturing an electrode substrate provided with a TFT element will be described below.

A chromium thin film is formed on an alkali-free glass substrate by sputtering, and the gate electrode is patterned by photolithography. Next, plasma CVD
Thereby, a silicon nitride film, an amorphous silicon film as an insulating film, and a silicon nitride film as an etching stopper are continuously formed. Next, the silicon nitride film serving as an etching stopper is patterned by photolithography. An n + amorphous silicon film is formed and patterned for the TFT terminal to make an ohmic contact with the metal electrode, and an ITO film to be a display electrode is formed and patterned. Further, aluminum is applied as a wiring material by sputtering, and signal wiring and a metal electrode of a TFT are formed by photolithography. Using the drain electrode and the source electrode as masks, the n + amorphous silicon film in the channel portion is removed by etching to obtain an electrode substrate provided with a TFT element. In the case of a reflective liquid crystal display element, the display electrode is made of a material having a high reflectance such as aluminum or silver.

A vertical alignment film is provided on a color filter. Similarly, a vertical alignment film is provided on an electrode substrate having a thin film transistor facing the same. A split alignment projection is provided on the opposing electrode substrate so as to correspond to the split alignment projection provided on the color filter. After the two substrates are bonded to each other using an epoxy adhesive as a sealant, a vertically aligned liquid crystal is injected from an injection port provided in the seal portion. After injecting the liquid crystal, the inlet is sealed, and a polarizing plate is attached to the outside of the substrate to manufacture a liquid crystal display device.

FIG. 2 shows an example of a plan view of the color filter of the present invention. A colored film is formed in the opening 10 of the black matrix 9. Trapezoidal stripe-shaped protrusion 1 whose cross section divides the long side direction of the black matrix opening into two.
1 is formed every other pixel. On the opposing electrode substrate, stripe-shaped protrusions are formed every other pixel so as to be alternately arranged with the stripe-shaped protrusions on the color filter.

The projection according to the present invention and the liquid crystal display device using the same include a personal computer, a word processor, an engineering workstation, a navigation system,
It is used for display screens of liquid crystal televisions and the like, and is also suitably used for liquid crystal projection and the like. Further, in the field of optical communication and optical information processing, it is suitably used as a spatial modulation element using a liquid crystal. A spatial modulation element modulates the intensity, phase, polarization direction, etc. of light incident on the element according to an input signal to the element, and is used for real-time holography, a spatial filter, incoherent / coherent conversion, and the like. It is.

[0066]

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

(Measurement of Volume Resistance Value) A target material is coated to a thickness of 1 μm on a glass substrate on which an aluminum thin film is deposited. One more diameter on the coating film
A 5 mm aluminum electrode is deposited. A direct current of 1 V was applied between the two electrodes sandwiching the coating film, and the volume resistance was determined from the current value and the thickness of the coating film 5 minutes after the application of the voltage.

Example 1 (Preparation of resin black matrix) 3, 3 ', 4, 4'
-144.1 g of biphenyltetracarboxylic dianhydride was mixed with 1095 g of γ-butyrolactone and 209 g of N-methyl-2-pyrrolidone, and 95.1 g of 4,4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldimethyl Add 6.2 g of siloxane and add 3 at 70 ° C.
After reacting for 2 hours, 2.96 g of phthalic anhydride was added and further reacted at 70 ° C. for 1 hour to obtain a polyimide precursor (polyamic acid) solution.

A carbon black mill base having the following composition was mixed with a homogenizer at 7000 rpm for 3 hours.
The mixture was dispersed for 0 minutes, and the glass beads were filtered to prepare a black paste.

Carbon black mill base Carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) 4.6 parts Polyimide precursor solution 24.0 parts N-methyl-2-pyrrolidone 61.4 parts Glass beads 90.0 parts 300 × 350 mm A black paste was applied on a non-alkali glass (OA-2, manufactured by NEC Corporation) substrate having a size of
For 20 minutes. Subsequently, a positive photoresist ("Microposit" SRC100 30 cp manufactured by Shipley Co., Ltd.) was applied by a spinner and dried at 90 ° C. for 10 minutes. The photoresist film thickness was 1.5 μm. Exposure was performed through a photomask using an exposure machine PLA-501F manufactured by Canon Inc.

Next, an aqueous solution containing 2% by weight of tetramethylammonium hydroxide at 23 ° C. was used as a developer.
The substrate was dipped in a developing solution, and at the same time, the substrate was swung so as to make one reciprocation in a width of 10 cm in 5 seconds, thereby simultaneously developing the positive photoresist and etching the polyimide precursor. The development time was 60 seconds. Thereafter, the positive type photoresist was peeled off with methylcellosolve acetate, and further cured at 300 ° C. for 30 minutes. Thus, the film thickness is 0.90 μm, and the opening is 240 μm in the vertical direction.
m, a grid-like black matrix of 60 μm in the horizontal direction was provided. The OD value of the black matrix was 3.0.

(Formation of Coloring Layer) Dianthraquinone pigment represented by Color Index No. 65300 Pigment Red 177 as a red, green and blue pigment, Color Index No. 74265 Pig
A phthalocyanine green pigment represented by ment Green 36 and a phthalocyanine blue pigment represented by Color Index No. 74160 Pigment Blue 15-4 were prepared. The above pigments were mixed and dispersed in the polyimide precursor solution 1 used for the black matrix, respectively, to obtain three kinds of colored pastes of red, green and blue. First, a blue paste was applied on a resin black matrix substrate and semi-cured at 120 ° C. for 20 minutes. Then, a positive photoresist ("Miley" manufactured by Shipley Co., Ltd.)
croposit "SRC100 30cp) with spinner, 90 ℃
For 10 minutes. Exposure was performed using a photomask, and while the substrate was immersed and rocked in a 2% by weight aqueous solution of tetramethylammonium hydroxide, development of a positive photoresist and etching of a polyimide precursor were simultaneously performed. Thereafter, the positive type photoresist was peeled off with methyl cellosolve acetate, and a blue colored layer having a width of about 90 μm and a stripe shape in the vertical direction was formed at a pitch of 300 μm in the width direction. Furthermore, it was cured at 300 ° C. for 30 minutes. The thickness of the blue coloring layer was 1.2 μm.

After the substrate was washed with water, striped green and red colored layers were formed in the same manner as the blue colored layer, and the pixel spacing of the three colors was 10 pixels.
It was formed to have a thickness of μm.

Next, a transparent protective layer was laminated. As a protective layer, acetic acid was added to methyltrimethoxysilane and hydrolyzed to obtain an organosilane condensate. 3,3 ', 4,4'
-Benzophenonetetracarboxylic dianhydride and 3-aminopropyltriethoxysilane are mixed in an N-methyl-2-pyrrolidone solvent at a molar ratio of 1: 2,
The reaction was performed to obtain a condensate having an imide group. A composition obtained by mixing the organosilane mixture, the condensate having an imide group, and N-methyl-2-pyrrolidone at a weight ratio of 5: 2: 4 is formed into a black matrix and a coloring layer of three primary colors. The resultant was coated on the substrate and cured to obtain a 1.0 μm thick transparent protective layer made of a polyimide-modified silicone polymer.

On the substrate on which the transparent protective layer was formed, a film thickness of 150 nm and a surface resistance of 20 Ω /
The ITO film of □ was formed.

(Formation of Division Orientation Protrusion) 1,4-butanediol-bis (3-aminopropyl) ether 16
3.4 g (0.80 mol), 120.2 g (0.60 mol) of 4,4'-diaminodiphenyl ether, 3,3 '
124.1 g of diaminodiphenylsulfone (0.5
0 mol) and 24.9 g (0.10 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane together with 1944 g of N-methyl-2-pyrrolidone and 1944 g of γ-butyrolactone, and stirring the mixture. 315.8 g (0.98 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 218.0 g (1.00 mol) of pyromellitic dianhydride were added, and the mixture was heated at 83 ° C. for 3 hours. After reacting for an hour, 3.92 g (0.04 mol) of maleic anhydride was added, and the mixture was further added at 83 ° C for 3 hours.
Allowed to react for hours. Thus, a polyimide precursor solution 2 having a concentration of 20% by weight and a viscosity of 1.3 poise was obtained.

A paste for projections having the following composition was dispersed at 7000 rpm for 30 minutes using a homogenizer.
The paste for protrusions was prepared by filtering the glass beads.

Barium sulfate (BF-20, manufactured by Sakai Chemical Industry Co., Ltd.) 45.0 parts Polyimide precursor solution 2 142.5 parts N-methyl-2-pyrrolidone 115.0 parts γ-butyrolactone 115. 0 parts 3-methyl-3-methoxybutanol acetate 63.8 parts Glass beads 481.3 parts This paste was filtered with a filter having a pore size of 1.0 μm to prepare a coating liquid. This coating solution was applied on the color filter by a spin coater and semi-cured in a hot air dryer at 145 ° C. for 20 minutes to form a 1.8 μm coating film. Thereafter, a positive photoresist is applied, and 90 ° C.
For 10 minutes. Photoresist thickness 1.5μ
m. Exposure was performed through a photomask using an exposure machine PLA-501F manufactured by Canon Inc.

Next, an aqueous solution containing 2% by weight of tetramethylammonium hydroxide at 23 ° C. was used as a developer.
The substrate was dipped in a developing solution, and simultaneously, the substrate was swung so as to make one reciprocation in a width of 10 cm in 5 seconds, thereby simultaneously developing the photoresist and etching the polyimide precursor. The development time was 80 seconds. The photoresist was stripped with a methylcellosolve, and then cured at 250 ° C. for 30 minutes to form a 1.5 μm-thick striped projection for divisional orientation.

The stripe-shaped projection has a lower side of 15 μm in cross section.
m, the trapezoid having an upper side of 14 μm. Further, the in-plane variation of the lower side of the projection was within a range of 15 ± 1 μm, and no chipping or disconnection was observed, which was favorable. As shown in FIG. 2, the stripe-shaped protrusions are arranged every other pixel at positions that bisect the long side of one pixel, and penetrate the entire display portion of the color filter.

Thus, the color filter of the present invention was obtained. The volume resistance of the protrusion was 10 ¹³ Ωcm.

(Preparation of Electrode Substrate) A chromium thin film was formed on an alkali-free glass substrate by sputtering, and was patterned into a gate electrode by photolithography. Next, the thickness of the insulating layer is 700 n by plasma CVD.
A silicon nitride film having a thickness of 100 nm, an amorphous silicon film having a thickness of 100 nm as a channel layer, and a silicon nitride film having a thickness of 500 nm were successively formed as an etching stopper layer. Next, the silicon nitride film of the etching stopper layer was patterned by photolithography. An n + amorphous silicon film for forming an ohmic contact between the TFT terminal and the metal electrode was formed. An ITO film serving as a display electrode was formed thereon and patterned. Further, a film of aluminum as a wiring material was formed by sputtering, and signal wiring and a metal electrode of a TFT were formed by photolithography. Using the drain electrode and the source electrode as a mask, the n + amorphous silicon film in the channel portion was removed by etching to obtain an electrode substrate having a TFT element.

(Production and Evaluation of Color Liquid Crystal Display) A vertical alignment film was provided on the color filter of the present invention. Regarding the opposing electrode substrate, 1
Stripe-like protrusions similar to the stripe-like protrusions on the color filter were arranged for each pixel. However, the stripe-shaped projections were alternately arranged with the stripe projections on the color filter for each pixel when they were bonded to the color filter. Similarly, a vertical alignment film was provided on the electrode substrate provided with the opposed thin film transistor.
(The order of the text was corrected.) After bonding these two substrates using an epoxy adhesive as a sealant, a vertically aligned liquid crystal was injected from an injection port provided in the seal portion. After injecting the liquid crystal, the injection port was sealed, and a polarizing plate was attached to the outside of the substrate to produce a liquid crystal display device.

This liquid crystal display had good display quality, had no problem in the orientation of the liquid crystal, and had a viewing angle of 140 ° or more.

Example 2 A paste having the following composition was prepared as a projection paste, and a liquid crystal display device was produced in the same manner as in Example 1 except for this.

The stripe-shaped projection has a lower side of 12 μm in cross section.
m, the trapezoid having an upper side of 10 μm. Further, the in-plane variation of the lower side of the protrusion was within a range of 12 ± 1 μm, and no chipping or disconnection was observed, which was favorable. The volume resistance of the protrusion is 10 ¹³ Ωc
m. As shown in FIG.
Every other pixel is arranged at a position that bisects the long side of the pixel, and penetrates the entire display portion of the color filter.

This liquid crystal display device exhibited good display quality, had no problem in the orientation of the liquid crystal, and had a viewing angle of 140 ° or more.

Paste for projection Dianthraquinone red pigment (Pigment Red 177) 30.0 parts Polyimide precursor solution 2 225.0 parts N-methyl-2-pyrrolidone 90.6 parts γ-butyrolactone 90.6 parts 3-methyl -6-methoxybutanol acetate 63.8 parts Glass beads 481.3 parts Example 3 Color index No. 65300 Pig as red, green and blue pigments
Colo, a dianthraquinone pigment represented by ment Red 177
r Index No.74265 Pigment Green 36, phthalocyanine green pigment, Color Index No.74160 Pigme
A phthalocyanine blue pigment represented by nt Blue 15-4 was prepared.

6 g of an acrylic copolymer resin powder in which styrene: methyl methacrylate: methacrylic acid = 30: 30: 40, 6 g of trimethylolpropane triacrylate as a polyfunctional monomer, and a photopolymerization initiator (Irgacure manufactured by Ciba Specialty Chemicals) "369) Each of the above pigments was mixed and dispersed in a cyclopentanone solution containing 3 g to obtain three types of colored pastes of red, green and blue.

A blue paste was applied on a resin black matrix substrate produced in the same manner as in Example 1, and dried with hot air at 80 ° C. for 10 minutes. Exposure using a photomask,
The substrate was dipped in an alkali developer and developed while simultaneously rocking the substrate. Then, it was cured at 220 ° C. for 30 minutes. The thickness of the blue coloring layer was 1 μm.

After the substrate was washed with water, it was treated in the same manner as the blue colored layer
Green and red colored layers were formed. Black matrix and red,
An ITO having a thickness of 150 nm and a surface resistance of 20 Ω / □ is formed on the substrate on which the blue and green coloring layers are formed by sputtering.
A film was formed.

The red paste used for forming the red colored layer was applied on the ITO film and dried with hot air at 80 ° C. for 10 minutes.
Exposure was performed using a photomask, and the substrate was immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and simultaneously developed while oscillating the substrate. The development time was 60 seconds. Next, the resultant was cured at 220 ° C. for 30 minutes to form a stripe-shaped projection for divisional alignment having a thickness of 1 μm.

The stripe-shaped projection has a lower side of 15 μm in cross section.
m, the trapezoid having an upper side of 14 μm. Further, the in-plane variation of the lower side of the projection was within a range of 15 ± 1 μm, and no chipping or disconnection was observed, which was favorable. As shown in FIG. 2, the stripe-shaped protrusions are arranged every other pixel at positions that bisect the long side of one pixel, and penetrate the entire display portion of the color filter.

Thus, the color filter of the present invention was obtained. The volume resistance of the protrusion formed by the red paste is 1
It was 0 ¹² Ωcm.

In the same manner as in Example 1, the color filter and the electrode substrate were bonded, and liquid crystal injection, injection port sealing, and polarizing plate bonding were performed to manufacture a liquid crystal display device.

This liquid crystal display device exhibited good display quality, had no problem in the orientation of liquid crystal, and had a viewing angle of 140 ° or more.

Example 4 Instead of forming a black matrix, a portion having reduced transmittance was formed by applying a colored layer repeatedly. That is, red, blue, and green coloring layers are formed on an alkali-free glass substrate having no black matrix in the same manner as in Example 1, and at this time, two pixels are filled between two adjacent pixels filled with the black matrix. It was filled with a layer of colored coloring material.

Further, in the same manner as in Example 1, a transparent protective layer was provided, an ITO layer was formed, and then the projections for division orientation were formed using the projection paste used in Example 1. The stripe-shaped protrusions were trapezoidal with a lower side of the cross section of 15 μm and an upper side of 14 μm. The in-plane variation of the lower side of the protrusion is 15 ± 1μ.
m, which was good without chipping or disconnection. The volume resistance of the protrusion was 10 ¹³ Ωcm.

In the same manner as in Example 1, the color filter was bonded to the electrode substrate, and the liquid crystal was injected, the injection port was sealed, and a polarizing plate was bonded, to produce a liquid crystal display device.

This liquid crystal display had good display quality, had no problem in the orientation of the liquid crystal, and had a viewing angle of 140 ° or more.

Example 5 A black matrix, a colored layer,
A transparent protective film and an ITO layer were formed. A projection paste having the following composition was applied on the ITO layer and semi-cured at 120 ° C. for 20 minutes. Subsequently, a positive photoresist was applied and dried at 80 ° C. for 20 minutes. Exposure using a photomask, 2% by weight of tetramethylammonium hydroxide
By immersing in an aqueous solution, the development of the photoresist and the etching of the polyimide precursor were simultaneously performed. The development time was 60 seconds. The photoresist was peeled off with methylcellosolve acetate, and cured at 300 ° C. for 30 minutes to form a 1 μm-thick projection for division alignment having the same pattern as in Example 1.

The stripe-shaped projection has a lower side of 15 μm in cross section.
m, the trapezoid having an upper side of 14 μm. Further, the in-plane variation of the lower side of the projection was within a range of 15 ± 1 μm, and no chipping or disconnection was observed, which was favorable.

Projection paste carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) 4.6 parts Polyimide precursor solution 1 24.0 parts N-methyl-2-pyrrolidone 61.4 parts Glass beads 90.0 parts Split orientation Volume resistance value of the black colored layer on which the projections are formed is 10
It was ⁹ Ωcm.

In the same manner as in Example 1, the color filter and the electrode substrate were bonded together, and liquid crystal injection, sealing of the injection port, and bonding of a polarizing plate were performed to manufacture a liquid crystal display device.

This liquid crystal display had good display quality, had no problem in the orientation of the liquid crystal, and had a viewing angle of 140 ° or more.

Comparative Example 1 Using only the polyimide precursor solution 2 used in the projection paste of Example 1, an attempt was made to form a projection for split orientation so as to have a film thickness of 1.5 μm. However, even when the development time was shortened to 40 seconds or less in the etching of the polyimide precursor 2, a large number of disconnections of the stripe-shaped projections were observed due to high solubility in the developing solution. The in-plane variation of the lower side of the protrusion was 15 ± 3 μm.

Thus, when a liquid crystal display device was manufactured,
Poor display was observed due to poor alignment of the liquid crystal.

[0108]

As described above, the liquid crystal display device of the present invention has projections for dividing and aligning the liquid crystal, so that the display quality is excellent and a wide viewing angle can be achieved. Further, since the projections can be formed stably, a liquid crystal display device which is excellent in productivity and free from display defects can be provided.

[Brief description of the drawings]

FIG. 1 is an example of a cross-sectional view of a color filter substrate having a projection for split alignment according to the present invention.

FIG. 2 is an example of a plan view of a color filter substrate having a projection for division alignment according to the present invention.

[Explanation of symbols]

 1: Glass substrate 2, 9: Black matrix 3: Blue coloring layer 4: Red coloring layer 5: Green coloring layer 6: Transparent protective layer 7: Transparent conductive layer 8, 11: Projection for split alignment 10: Opening

Claims (7)

[Claims] 1. A divisional alignment substrate used for liquid crystal display, wherein a projection formed on the substrate surface for liquid crystal divisional alignment is composed of at least a filler and a resin. Substrate for alignment. 2. The substrate according to claim 1, wherein the filler is at least one selected from the group consisting of barite, barium sulfate, barium carbonate, calcium carbonate, silica and talc. 3. The substrate for split orientation according to claim 1, wherein the volume resistivity of the protrusion is 10 ⁷ Ωcm or more. 4. The substrate for split alignment according to claim 1, wherein the resin forming the protrusion is a polyimide resin or an acrylic resin. 5. The substrate for split alignment according to claim 1, wherein the substrate for split alignment is a color filter substrate. 6. The split alignment substrate according to claim 1, wherein the split alignment substrate is an electrode substrate. 7. A liquid crystal display device using the substrate for split alignment according to claim 1.