JP2003241177A - Manufacturing method for electrode substrate of color liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily fabricating an electrode substrate for a color liquid crystal display device provided with a colored layer directly on a TFT substrate without any problem of quality. <P>SOLUTION: The formation of the colored layer on the electrode substrate for the color liquid crystal display device includes (a) a wettability variation layer forming process of providing a wettability variation layer with low wettability to a material (coloring ink) for forming the colored layer on the TFT substrate so that an area where at least the colored layer is provided is included, (b) a selective exposing process of exposing an area part corresponding to the colored layer formation area of the wettability variation layer selectively to ultraviolet rays to make only the exposed area high in wettability to the material (coloring ink) for forming the colored layer, and (c) a process of forming the colored layer in the area made high in wettability by an ink jetting method. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing an electrode substrate in a color liquid crystal display device and an electrode substrate, and more particularly to a method of forming a color filter layer on the electrode substrate in a color liquid crystal display device.

[0002]

2. Description of the Related Art In recent years, LCDs (Liquid Cryes)
Tal display) is becoming more and more popular,
Since it has good visibility and is suitable for color display and moving image display, it is suitable for TFT (Thin Film Transistor).
or) is arranged in each pixel unit as an active element, whereby a voltage is independently applied to the liquid crystal in each pixel area to make the pixel bright and dark, and there are many driving methods called an active matrix method for displaying an image or character information. It is used. An active matrix system using such a TFT is also called a TFT drive system. A TFT is a transistor formed in a semiconductor thin film deposited on an insulating substrate such as glass. To form a display panel, several hundred thousand to one million TFTs corresponding to the number of pixels are arranged. T
An FT matrix is required, and in the case of color display, each pixel is composed of three color pixels of red, green, and blue, and therefore, a triple TFT is required. The TFT matrix is thus a kind of VLSI, and it can be said that the active matrix type liquid crystal display panel using TFT is a new technology in which the miniaturization-oriented VLSI technology and the large-area-oriented display technology are integrated.

5A and 5B are views for explaining an active matrix type liquid crystal display device as a conventional example 1, FIG. 5A is a schematic view thereof, and FIG. 5B is a sectional view of a pixel portion thereof. In a conventional liquid crystal display device, a T having a pixel driving TFT is used.
An FT substrate 501, a CF substrate 502 having a color filter (hereinafter referred to as CF), and a liquid crystal 503 sandwiched between them.
Composed of. The TFT substrate 501 is the TFT glass substrate 5
On 04, a scanning line 505 for selecting a pixel to write a signal,
A signal line 506 having a writing signal, a TFT 507 for driving a pixel at an intersection of the signal line 506, and a pixel electrode 508 connected to the TFT 507 are provided. Further, the CF substrate 502 on the display surface is arranged on the CF glass substrate 513, on each color filter 509 corresponding to each pixel having three primary colors of R, G, and B, and on the TFT and the TFT 507 which shields the light leakage region. A black matrix (BM) 510 and a counter electrode 512.

The liquid crystal 503 sandwiched between the TFT substrate 501 and the CF substrate 502 has a characteristic that it is arranged in the electric field direction between the pixel electrode 508 and the counter electrode 512, and by utilizing this characteristic, the pixel electrode 508 and the counter electrode 512. Gradation display is performed by the voltage between them. In contrast to these conventional liquid crystal display devices, the on-chip color filter structure in which a color filter is provided on the TFT substrate side is
JP-A-8-122824, JP-A-9-29263
It is disclosed in Japanese Patent No. In this on-chip color filter structure, since the color filter overlaps with each pixel electrode, no parallax occurs between the two and the aperture ratio of the pixel portion can be increased. Further, since there is almost no alignment error between the pixel electrode and the color filter, there is an effect that a high aperture ratio can be maintained even if the pixel portion is miniaturized.

FIG. 6 shows an example of an on-chip color filter, showing a unit pixel portion having a structure, (a) is a sectional view thereof, (b) is a plan view thereof, and (c) is a C diagram.
It is a top view except the F / BM portion. TFT substrate 601
Is a scanning line 605 for selecting a pixel to which a signal is to be written and a signal line 606 having a signal to be written on the TFT glass substrate 604.
And a TFT 607 which drives a pixel at the intersection thereof. Of these, the TFT 607 includes a gate electrode 620 provided on the TFT glass substrate 604, a gate insulating film 621 provided so as to cover the gate electrode 620, a semiconductor layer 622 formed on the gate insulating film 621, and a source. An electrode 623 and a drain electrode 624, and a passivation film 625 provided so as to cover all of them.

The scanning line 605 is connected to the gate electrode 620 and the signal line 606 is connected to the source electrode 623. A color filter 609 and a black matrix 610 are provided on the passivation film 625, and an overcoat film 611 that protects them is further formed. A pixel electrode 608 is provided on the overcoat film 611,
It is connected to the source electrode 624 of the TFT through the contact hole 626. The pixel electrode 608 is a signal line 606 and a scanning line
By overlapping with 605, light leakage around the pixel electrode 608 is prevented. In addition, the overcoat film 61
An alignment film (not shown) for controlling the alignment and tilt (pretilt) of the liquid crystal molecules 630 suitable for the liquid crystal operation mode is provided on the 1 and pixel electrodes 608, and the alignment is performed from the TFT glass substrate 604. Depending on the components up to the film, TFT
A substrate 601 is formed. The counter substrate 602 is provided with a counter electrode 612 and an alignment film (not shown) on a counter glass substrate 613, and the counter substrate 602 is formed by the components from the counter glass substrate 613 to the alignment film. There is.

Further, the TFT substrate 601 and the counter substrate 6
02 and the liquid crystal layer 603 sandwiched therebetween form one liquid crystal element. As a method for forming the colored layer, a dyeing method,
A pigment dispersion method, a printing method and the like are known. The dyeing method is a method in which a photosensitive resist is applied, patterning is performed by photolithography, and then dyeing is performed.The pigment dispersion method is a method in which a photosensitive resist in which a pigment is dispersed is applied,
It is patterned by photolithography technology. In the printing method, an ink containing a pigment is printed by an intaglio method, a letterpress method or a silk screen method.
However, the method using the dyeing method or the pigment dispersion method requires a photolithography process 1 to 3 times, which is problematic in terms of yield and cost. When using the printing method,
Although the photolithography process is eliminated, there are problems that it is difficult to obtain a highly accurate pattern and the flatness of the surface is impaired.

[0008]

Under the circumstances, the present invention provides an electrode substrate for a color liquid crystal display device in which a colored layer is directly provided on the TFT substrate side, easily and in terms of quality. It is intended to provide a method that can be produced without any problem.

[0009]

A method for manufacturing an electrode substrate in a color liquid crystal display device according to the present invention is a first electrode substrate in which a transparent common display electrode for pixel display is formed on one surface of a transparent base substrate. And a second element in which an active element made of a semiconductor thin film is provided for each pixel in a matrix on one surface of a transparent base substrate, and a transparent pixel display electrode capable of applying a voltage to the active element is provided for each pixel. An electrode substrate, and a first electrode substrate and a second electrode substrate,
The common display electrode and the pixel display electrode are arranged so as to face the liquid crystal so as to face each other with the liquid crystal interposed therebetween, and the liquid crystal between the pixel display electrode and the common electrode is used as a switching element. An active matrix color liquid crystal display device in which a voltage is selectively applied between a common display electrode of an electrode substrate and a pixel display electrode of a second electrode substrate to control transmitted light for each pixel. A method of manufacturing an electrode substrate in a color liquid crystal display device, wherein a colored layer for color display is integrally provided on the electrode substrate of No. 2, wherein the formation of the colored layer on the electrode substrate is (a) at least coloring. A wettability changing layer forming step of providing a wettability changing layer having low wettability with respect to a material for forming a colored layer (also referred to as a coloring ink) so as to include a region where a layer is provided;
(B) a selective exposure step of selectively exposing a region portion of the wettability changing layer corresponding to the colored layer forming region to increase the wettability of the material for forming the colored layer only in the exposed region. And (c) forming a colored layer in a region having high wettability.

Further, the method of manufacturing an electrode substrate in a color liquid crystal display device of the present invention comprises: a first electrode substrate having a transparent common display electrode for pixel display formed on one surface of a transparent base substrate; A second electrode substrate in which active elements made of a semiconductor thin film are provided for each pixel on one surface of a base substrate and arranged in a matrix, and transparent pixel display electrodes to which a voltage can be applied by the active element are provided for each pixel; And the first electrode substrate and the second electrode substrate are arranged so as to face each other with the common display electrode and the pixel display electrode facing the liquid crystal side, and the pixel display electrode and the common electrode are disposed. The liquid crystal in between is used as a switching element to selectively apply a voltage between the common display electrode of the first electrode substrate and the pixel display electrode of the second electrode substrate by the active element to transmit the transmitted light for each pixel. A method for manufacturing an electrode substrate in a color liquid crystal display device, which is a controlled active matrix type color liquid crystal display device and in which a light shielding layer for color display is integrally provided on the second electrode substrate. Then, the formation of the light-shielding layer on the electrode substrate includes (a) a wettability changing layer having low wettability with respect to a material (light-shielding ink) for forming the light-shielding layer so as to include at least a region where the light-shielding layer is provided. A wettability changing layer forming step to be provided, and (b) a region portion corresponding to the light shielding layer forming region of the wettability changing layer is selectively exposed to a material for forming the light shielding layer only in the exposed region. A selective exposure step for enhancing wettability, (c)
And a step of forming a light shielding layer in a region having high wettability, the method for manufacturing an electrode substrate in a color liquid crystal display device.

Further, in the above, the method is characterized by including a step of removing the wettability changing layer other than the portion where the colored layer and / or the light shielding layer is formed after the step of forming the colored layer and / or the light shielding layer. Further, in the above, in the selective exposure step, selective exposure is performed through a photomask having at least a photocatalyst-containing layer, whereby only the exposed region is wet with a material for forming a coloring layer and / or a light-blocking layer. It is characterized by increasing the sex.
Further, in the above, the step of forming the colored layer and / or the light shielding layer is an inkjet method. In addition, in the above, in the active matrix type color liquid crystal display device, an active element is a TFT (Thin Film Transistor).
And a method for manufacturing an electrode substrate in a color liquid crystal display device.

The wettability referred to here is the wettability with respect to the material (coloring ink, light-shielding ink) for forming the colored layer and / or the light-shielding layer, and only the dispersive component such as a saturated hydrocarbon liquid is used. Evaluation based on the contact angle of liquids that have hydrogen bonds such as water, liquids that have hydrogen bonds such as water, and liquids such as methylene iodide that have polar components and other dispersive force components, the surface free energy of the solid surface, and the critical surface tension of the solid. it can. In the present invention, a material (coloring ink, light-shielding ink) for forming a colored layer and / or a light-shielding layer is formed on a portion having high wettability on a wettability layer on which a pattern having high and low wettability is formed, When deposited by the inkjet method, the material wets and spreads over the high wettability part,
It does not squeeze out on the parts with low wettability.

[0013]

The method of manufacturing the electrode substrate in the color liquid crystal display device according to the present invention has the above-mentioned structure.
As a method for manufacturing an electrode substrate in a color liquid crystal display device in which a colored layer is directly provided on a T substrate, it is possible to provide a method that can be easily manufactured without any problem in terms of quality. Specifically, the pixel of the second substrate is formed so that the formation of the coloring layer and / or the light-blocking layer on the second substrate having the active element and the pixel display electrode includes at least a region where the coloring layer and the light-blocking layer are provided. The wettability changing layer forming step of providing a low wettability changing layer on the display electrode, and the area of the wettability changing layer corresponding to the colored layer and the light-shielding layer forming area are selectively exposed to ultraviolet light to expose. This is achieved by having a selective exposure step of increasing the wettability only in the exposed area and a step of forming a colored layer or a light shielding layer in the area of the increased wettability by an ejection method. That is, by selectively irradiating the colored layer forming region and the light shielding layer forming region of the wettability changing layer formed in each pixel display portion with light to increase the wettability of the surface, the colored ink is directly applied to the portion. Or a light-shielding ink is easily adhered, and a colored layer (color filter) of each color can be easily applied by spraying the coloring ink or the light-shielding ink onto the region having high wettability, especially by an inkjet method.
It is possible to form a light shielding layer (black matrix) in a predetermined position region. More specifically, the present invention provides a material for forming a colored layer (also referred to as a colored ink) or a light-shielding layer on a portion having high wettability on a wettability changing layer on which a pattern having high wettability is formed. When a material for forming (light-shielding ink) is applied by a discharge method, the material has a property that it wets and spreads over a portion with high wettability and does not spill out over a portion with low wettability. is there.

The present invention also provides, in the selective exposure step,
The property that the wettability change of the wettability change layer is achieved in a short time by utilizing the decomposition action of the photocatalyst by utilizing the selective exposure through the photomask having at least the photocatalyst containing layer is utilized. Further, since the wettability pattern is formed using the photomask with the photocatalyst, the electrode substrate itself in the color liquid crystal display device does not include the photocatalyst-containing layer, and therefore the pattern-formed body deteriorates over time due to the action of the photocatalyst. Don't worry about The electrode substrate in the color liquid crystal display device of the present invention, by having such a structure, can provide an electrode substrate for a color liquid crystal display device which can be easily manufactured without any problem in terms of quality.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION An example of an embodiment of a method for manufacturing an electrode in a color liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 1 is a process sectional view of a first embodiment of an electrode substrate in a color liquid crystal display device of the present invention, and FIG. 2 is a process sectional view of a second embodiment. FIG. 3 shows the first and second
FIG. 3 is a cross-sectional view of an example of an electrode substrate in the color liquid crystal display device manufactured by the embodiment of FIG. FIG. 4 is a diagram for explaining changes in the surface state of the photocatalyst-containing layer due to irradiation of ultraviolet rays. 1 to 4, 101 and 201 are base substrates and 102
And 202 are gates, 103 and 203 are gate insulating layers, 104 and
204 is Armofus silicon, 105 and 205 are drains, 1
06 and 206 are sources, 107 and 207 are passivation layers, 108 and 208 are wettability changing layers, 109 and 209 are ultraviolet rays,
Reference numerals 110 and 210 are photomasks with a photocatalyst, 111 and 211 are photocatalyst containing layers, 112 is a colored layer, 212 is a light shielding layer, and 313 is a pixel electrode.

First Embodiment First, an example of a first embodiment of a method for manufacturing an electrode substrate in a color liquid crystal display device of the present invention will be described with reference to FIGS. 1 and 3. In this example, a first electrode substrate in which a transparent common display electrode for pixel display is formed on one surface of a transparent base substrate, and an active element made of a semiconductor thin film is provided for each pixel on one surface of the transparent base substrate. And a second electrode substrate provided with a transparent pixel display electrode to which a voltage can be applied by an active element for each pixel, and the first electrode substrate and the second electrode substrate are provided. , The common display electrode and the pixel display electrode are arranged so as to face the liquid crystal side and face each other through the liquid crystal, and the liquid crystal between the pixel display electrode and the common electrode is used as a switching element, and , An active matrix color liquid crystal display device in which a voltage is selectively applied between a common display electrode of a first electrode substrate and a pixel display electrode of a second electrode substrate to control transmitted light for each pixel. And, a second substrate, a manufacturing method of the electrode substrate in a color liquid crystal display device is provided integrally with the colored layer for a color display.

First, a substrate is prepared in which TFTs, which are active elements made of a semiconductor thin film, are provided for each pixel on one surface of a transparent base substrate 101 and arranged in a matrix.
(FIG. 1A) As a transparent base substrate 101, usually,
A glass substrate is used. The TFT and its wiring portion can be formed by a known VLSI technique. Then, by selectively exposing the entire surface on the TFT formation side through a photomask having a photocatalyst containing layer, a wettability changing layer 108 having low wettability and having high surface wettability is applied. (FIG. 1 (b)) The wettability changing layer in the present invention means a layer in which the wettability of the surface is changed by the action of a photocatalyst at the time of exposure and a pattern can be formed by the site where the wettability is changed. The wettability changing layer is a wettability changing layer whose wettability changes so that the contact angle of the liquid is reduced by exposure. As a result, if pattern exposure or the like is performed, the wettability can be easily changed and a pattern of the ink-philic region having a small contact angle with the liquid can be formed.

In the unexposed portion, the wettability changing layer has a contact angle with a liquid having a surface tension of 40 mN / m of 10 degrees or more, preferably a contact angle with a liquid having a surface tension of 30 mN / m of 10 degrees. Above all, the contact angle with a liquid having a surface tension of 20 mN / m is preferably 10 degrees or more. This is because the unexposed portion is the portion that requires ink repellency in the present invention, so if the contact angle with the liquid is small, the ink repellency is insufficient and ink may remain. This is because it is not preferable because it causes a property. Further, the wettability changing layer has a reduced contact angle with a liquid when exposed to light and has a contact angle of 9 with a liquid having a surface tension of 40 mN / m.
It is preferable that the layer has a contact angle with a liquid having a surface tension of 50 mN / m of 10 degrees or less, particularly a contact angle with a liquid having a surface tension of 60 mN / m of 10 degrees or less. This is because if the contact angle of the exposed portion with the liquid is high, the spread of the ink in this portion may be poor.
The contact angle with the liquid here is measured by using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) with liquids having various surface tensions (from a microsyringe to a liquid). 30 seconds after dropping the droplet), the result was obtained, or the result was obtained as a graph. In addition, in this measurement, as a liquid having various surface tensions, wetting index standard liquid manufactured by Junsei Chemical Co., Ltd. was used.

The material used for such a wettability changing layer is not particularly limited as long as it is a material whose wettability is changed by the characteristics of the above-mentioned wettability changing layer, that is, the photocatalyst in the photocatalyst-containing layer contacted by exposure. It's not something
For example, (1) an organopolysiloxane that exhibits great strength by hydrolyzing and polycondensing chloro or alkoxysilane etc. by a sol-gel reaction, (2) an organopolysiloxane crosslinked with a reactive silicone having excellent water repellency and oil repellency. Organopolysiloxanes such as polysiloxanes can be mentioned. (3) A water repellent self-assembled film using fluoroalkylsilane or the like can be given.

In the case of the above (1), the general formula: Y _n SiX _(4-n) (wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group,
X represents an alkoxyl group, an acetyl group or halogen. n is an integer from 0 to 3. It is preferable that the organopolysiloxane is a hydrolysis-condensation product or a co-hydrolysis-condensation product of one or more silicon compounds represented by the formula (1). The number of carbon atoms of the group represented by Y is preferably within the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group or a butoxy group. preferable. In addition, a polysiloxane containing a fluoroalkyl group can be particularly preferably used, and a generally known fluorine-based silane coupling agent can be used. Specific materials and the like are described in detail in Japanese Patent Application Laid-Open No. 2000-249821 filed by the present inventors. Such a wettability changing layer can be formed by dispersing the above-mentioned components in a solvent together with other additives as necessary to prepare a coating liquid and applying the coating liquid onto a substrate. . In the present invention, the thickness of the wettability changing layer is
From the relationship of change rate of wettability by photocatalyst, 0.00
The thickness is preferably 1 μm to 1 μm, particularly preferably 0.01 to 0.1 μm.

Further, as the wettability changing layer, the above-mentioned screen is used.
By using a recone material, the wettability changing layer
Also functions as the passivation layer 107 on the TFT.
I can sleep. In this case, the manufacturing process is simplified.
It The photomask having the photocatalyst-containing layer of the present invention is
At least having a photocatalyst containing layer and a photomask
Any form will do as long as it is available. Usually a photomask
The photocatalyst-containing layer on the thin film formed by the prescribed method on top
It is made up of. In addition, this photocatalyst containing layer is
It may be formed in a turn shape. Such a photoma
As the disc, a glass plate made of metallic chrome
In addition, for printing purposes, use a plate-making film, etc.
You can The photocatalyst containing layer disperses the photocatalyst in the binder.
Can be formed. The photocatalyst also illuminates the binder
The binder is a photocatalyst because it may decompose due to excitation.
Must have sufficient resistance to the photooxidation effect of
It As a photocatalyst, oxidation known as an optical semiconductor
Titanium (TiO₂), Zinc oxide (ZnO), tin oxide
(SnO₂), Strontium titanate (SrTi
O₃), Fermented tungsten (WO₃), Bismuth oxide (B
i₂O₃), Iron oxide (Fe₂O ₃) From metal oxides such as
The photocatalyst is As photocatalysts,
Tan is preferred. Titanium oxide is a band gab ener
High energy, chemically stable, non-toxic and available
It's easy. As titanium oxide, anatase type and rutile
Both types can be used, but anatase type
Titanium oxide is preferred. As anatase type titanium,
Photocatalytic reactions occur more efficiently with smaller particles
Is preferred. An average particle size of 50 nm or less is preferred
And more preferably 20 nm or less. An example
For example, hydrochloric acid peptization type anatase type titania sol (from Ishihara
STS-02, average crystallite diameter 7 nm), nitric acid peptization type
Anatase-type titania sol (Nissan Chemical, TA-15,
The average crystallite diameter is 12 nm).

As the binder, a silicone resin whose main skeleton has a siloxane bond (-Si-O-) can be used. The silicone resin has an organic group bonded to a silicon atom, and as described in detail in Examples, when the photocatalyst is photoexcited, the organic group bonded to the silicon atom of the silicone molecule is replaced with an oxygen-containing group by photocatalysis. As a result, the wettability is improved, and therefore, it also functions as a substance that changes the wettability. As the silicone resin, a general formula Y _n Si
One or more hydrolytic condensates or co-hydrolytic condensates of silicon compounds represented by X _4-n (n = 0 to 3) can be used. Y can be an alkyl group, fluoroalkyl group, vinyl group, amino group, or epoxy group, and X can be a halogen, methoxyl group, ethoxyl group, or acetyl group.

Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltribromosilane. Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n
-Propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltrit-butoxysilane; n-
Hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltrit-butoxysilane; n-decyltrichlorosilane, n-decyl Tribromosilane,
n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-
Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n
-Octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl Triisopropoxysilane, phenyltri-t-butoxysilane; dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, Diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyl Diethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane;
Vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriisopropoxysilane, vinyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ
-Glycidoxybropyrtriisopropoxysilane, γ
-Glycidoxypropyltri-t-butoxysilane; γ-
Methacryloxypropylmethyldimethoxysilane, γ
-Methacryloxypropylmethyldiethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ
-Methacryloxypropyltriethoxysilane, γ-
Methacryloxypropyltriisopropoxysilane,
γ-methacryloxypropyltri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxysilane;
γ-mercaptopropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltriethoxysilane
t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; and their partial hydrolysates; and mixtures thereof can do.

When a binder layer made of organoalkoxysilane is used, at least 10 parts thereof are used.
More preferably, 30% by weight is composed of a bifunctional silicone precursor, for example dialkoxydimethylsilane. When the organoalkoxysilane is used in the sol-gel method or the like, the crosslink density can be improved by using a trifunctional silicone precursor such as trialkoxymethylsilane as a main component. As the binder, an amorphous silica precursor can be used and is represented by the general formula SiX ₄ , where X is a halogen, a methoxy group, an ethoxy group, an acetyl group or the like, a silicon compound, or a hydrolyzate thereof. Is a silanol,
Alternatively, polysiloxane having an average molecular weight of 3000 or less is preferable. Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. Further, in this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, and hydrolyzed by moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing film can be formed by dehydration condensation polymerization with. If dehydration polycondensation of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. These binders can be used alone or in combination of two or more.

Further, it is also possible to form a film by using titanium oxide alone without using a binder. In this case, amorphous titania is formed on the substrate and then fired to change the phase to crystalline titania. Amorphous titania is, for example, titanium tetrachloride, hydrolysis of titanium inorganic salt such as titanium sulfate, dehydration condensation, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetrabutoxy titanium, tetramethoxy titanium, etc. The organotitanium compound can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Then, it is converted to anatase type titania by firing at 400 ° C to 500 ° C, and 600 ° C to 700 ° C.
It can be transformed into rutile type titania by firing at ℃. Further, in the layer containing the photocatalyst and at least one of the organosiloxane and the amorphous silicidity, the amount of the photocatalyst is preferably 5% by weight to 60% by weight, 20
More preferably, it is from 40% by weight to 40% by weight. Also,
As a method for forming the photocatalyst-containing layer consisting of only the photocatalyst,
For example, a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum evaporation method can be used. By forming the photocatalyst-containing layer by the vacuum film formation method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, and this makes it possible to uniformly change the properties on the property change layer. Since it is possible and it consists only of a photocatalyst, it becomes possible to change the characteristic on a characteristic change layer more efficiently compared with the case where a binder is used.

The photocatalyst and the binder can be dispersed in a solvent to prepare a coating solution and applied. Examples of the solvent that can be used include alcohol-based organic solvents such as ethanol and isopropanol. Also,
Titanium-based, aluminum-based, zirconium-based, and chromium-based coupling agents can also be used. The photocatalyst-containing coating solution can be applied to the photomask by a method such as spray coating, dip coating, roll coating, or bead coating. When a UV-curable component is contained as a binder, a layer of the composition containing the photocatalyst can be formed on the base material by irradiating it with UV rays to carry out a curing treatment. The anatase-type titania has an excitation wavelength of 380 nm or less, and in the case of such a photocatalyst, it is necessary to excite the photocatalyst with ultraviolet rays. Mercury lamps, metal halide lamps, xenon lamps, excimer lamps, excimer lasers, YAG lasers, and other ultraviolet light sources can be used as those that emit ultraviolet light.

Next, the area portion of the wettability changing layer 108 corresponding to the colored layer forming area is selectively exposed to ultraviolet rays 109 through a photomask having a photocatalyst containing layer, and only the exposed area has high wettability. To do. (FIG. 1 (c)) Here, the reason why the wettability changing layer has a high wettability in the portion corresponding to the colored layer forming region by irradiation of ultraviolet rays is illustrated by an example in which the wettability changing layer is made of fluorine-based silicone. I will give you a brief explanation. In this case, as shown in FIG. 4A, the surface state with low wettability is covered by the CF ₃ group before the UV irradiation, but as shown in FIG. It is considered that the OH group is generated in the irradiation region by the irradiation, so that the wettability is changed only in the irradiation region to be high. Incidentally, the mechanism of action of the photocatalyst is not always clear, but the carrier generated by irradiation of light directly reacts with a nearby compound or oxygen,
It is believed that active oxygen species generated in the presence of water change the chemical structure of organic substances. Thus, in the present invention, by performing the exposure through the photocatalyst-attached photomask, the wettability change reaction of the wettability change layer is significantly promoted as compared with the exposure using only the photomask,
The resolution is improved because the reaction is completed by shortening the exposure time and further by exposing for a short time.

Next, a colored layer is formed on the region having high wettability by a discharge method. (FIG. 1 (d)) As an ejection method, there is a method of applying a predetermined aqueous colored layer to each color pixel portion by an inkjet method. With the inkjet nozzles arranged at a predetermined pitch, while controlling the ejection from each nozzle while relatively moving the substrate for electrode formation, it is relatively easy to apply a predetermined color to a predetermined position. be able to. Positioning for controlling the injection position to a predetermined position can be performed using a mark or the like. In this way, the colored layer (color filter) can be formed at the portion corresponding to each pixel of the electrode substrate on which the TFT is formed. Then, a light shielding layer is formed. As a method for forming the light-shielding layer, any patterning method that is usually carried out may be used, but a method using the above-mentioned inkjet, a photolithography method, or the like is preferable as in the coloring layer.

If necessary, the wettability changing layer at the contact hole portion is removed. The removal method is
Although depending on the material of the wettability changing layer, for example, when the material of the wettability changing layer is silicone, an alkaline developer or the like can be used. Moreover, you may form an overcoat film by apply | coating, exposing, developing, and baking an overcoat layer as needed. Finally, a pixel electrode is formed by forming a film of indium tin oxide (ITO), which is a transparent electrode, and patterning it. After that, an alignment film is applied, and after rubbing treatment, it is bonded to the counter substrate with a predetermined gap. Liquid crystal is injected into this space with a light-shielding layer on the side surface and a spacer interposed therebetween, and an active matrix type liquid crystal display device is completed.

[Second Embodiment] An example of a second embodiment of a method for manufacturing an electrode substrate in a color liquid crystal display device of the present invention will be described with reference to FIGS. 2 and 3. First, a transparent base substrate
TF which is an active element made of a semiconductor thin film on one surface
A substrate in which T10 is provided for each pixel and arranged in a matrix is prepared. (FIG. 2A) A glass substrate is usually used as the transparent base substrate 11. The tTFT 10 and its wiring portion can be formed by a known VLSI technique. Then, the wettability changing layer 20 having low wettability, which has high wettability on the surface, is applied by selective exposure through a photomask having a photocatalyst-containing layer on the entire surface on the TFT 10 formation side. (FIG. 2B) As the wettability changing layer and the photocatalyst containing layer, the same ones as in the first embodiment can be used.

Next, the area portion of the wettability changing layer 20 corresponding to the light-shielding layer forming area is selectively exposed to ultraviolet light 35 through a photomask having a photocatalyst containing layer, and only the exposed area has high wettability. To do. (FIG. 2C) Here, the reason why the wettability of the portion of the wettability changing layer corresponding to the light-shielding layer formation region is increased by the irradiation of ultraviolet rays has been described in the first embodiment, and therefore will be omitted here. Next, a light-shielding layer is formed in a region having high wettability by a discharge method.
(FIG. 2 (d)) As an ejection method, a method of providing a predetermined light-shielding layer between the pixels of each color by an inkjet method can be mentioned. In a state where the jet nozzles of the ink jet are arranged at a predetermined pitch, the jet from each nozzle can be relatively easily sprayed at a predetermined position by controlling the jet from each nozzle while moving the substrate for electrode formation relatively. Positioning for controlling the injection position to a predetermined position can be performed using a mark or the like. In this way, the light-shielding layer (black matrix) can be formed on the area corresponding to each pixel of the electrode substrate on which the TFT is formed.

Next, a colored layer is formed. As a method for forming the colored layer, any patterning method that is usually carried out may be used, but a method using an inkjet, a photolithography method, or the like is preferable as in the case of the light shielding layer. Further, the wettability changing layer in the contact hole portion is removed as needed. As a method of removing, for example,
Examples thereof include alkaline developers. Moreover, you may form an overcoat film by apply | coating, exposing, developing, and baking an overcoat layer as needed. Finally, indium tin oxide (IT
O) is deposited and patterned to form a pixel electrode. After that, an alignment film is applied, and after rubbing treatment, it is bonded to the counter substrate with a predetermined gap. Liquid crystal is injected into this space with a light-shielding layer on the side surface and a spacer interposed therebetween, and an active matrix type liquid crystal display device is completed.

[0033]

(Embodiment 1) This embodiment is the first embodiment shown in FIGS.
In the example of Embodiment 1, a TFT and a transparent ITO pixel electrode are provided on one surface of a heat-resistant expansion glass substrate having a thickness of 1.1 mm at a pitch of 120 μm in length and a pitch of 320 μm in width of 360 mm ×
Using a substrate for a color liquid crystal display device (FIG. 1A) provided in an area of 465 mm, an electrode substrate provided with a colored layer for color display was produced. 1 and 3
It will be described based on. 0.5 g of organosiloxane (manufactured by Toshiba Silicone, TSL8113), fluoroalkoxysilane MF-160E (manufactured by Tochem Products) 0.
3 g and 0.2 g of 0.1 N hydrochloric acid were mixed and stirred for 24 hours. This solution was applied to a substrate for a color liquid crystal display device (see FIG. 1).
(A) It was applied on the entire surface. This was dried to cause hydrolysis and polycondensation reaction to form a transparent layer 108 having a film thickness of 0.1 μm. (FIG. 1B) Next, a predetermined photocatalytic inorganic coating agent ST-K01
(Photo by Ishihara Sangyo)
The region of the wettability changing layer 108 where the colored layer is formed was irradiated with ultraviolet rays 109.

The UV irradiation was carried out using a UV exposure machine MA-1200DUV manufactured by Dainippon Screen Co., Ltd. at 23.6 m.
Irradiation was performed for 3 minutes with an illuminance of W / cm ² . After making a predetermined region of the wettability changing layer ink-philic by irradiation of ultraviolet rays, a predetermined amount of colored ink, which becomes a color filter for color display, is made to be a predetermined amount by an inkjet discharge device in the ink-philic region. It was discharged to the pixel area. The colored ink wetted and spread on the exposed area and did not spill out on the unexposed area. This was dried and ultraviolet-cured to complete an electrode substrate having a colored layer (color filter) formed thereon.
The relative position between the inkjet and the base substrate 101 is
It was performed using a mark formed from a pattern for a positioning mark provided in advance on the photomask 110 used for the irradiation of the ultraviolet rays. Regarding the wettability changing layer,
The contact angle of water when not exposed to ultraviolet rays was 112 °, and the contact angle of water when it became ink-philic after exposure was 10 ° or less. As coloring inks, pigments of each color, solvent, UV
An oil-based ink composed of a curable resin, a polymerization initiator and a solvent was used. When a color liquid crystal display device was manufactured using the electrode substrate manufactured in this way, the display image quality was good.

(Example 2) Similar to Example 1, a wettability changing layer was formed on the entire surface of a substrate for a color liquid crystal display device. This was passed through a photomask (without a photocatalyst-containing layer) in Example 1
When exposed in the same manner, a predetermined area of the wettability changing layer became ink-philic in 120 minutes.

[0036]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, an electrode substrate for a color liquid crystal display device, in which a colored layer is directly provided on a TFT substrate as shown in FIG. 3, can be easily manufactured without any problem in quality. It is possible to provide a possible method.

[Brief description of drawings]

FIG. 1 is a process cross-sectional view of a first embodiment of a method for manufacturing an electrode substrate in a color liquid crystal display device of the present invention.

FIG. 2 is a process sectional view of a second embodiment of a method for manufacturing an electrode substrate in a color liquid crystal display device of the present invention.

FIG. 3 is an example of an electrode substrate manufactured by a method for manufacturing an electrode substrate in a color liquid crystal display device of the present invention.

FIG. 4 is a diagram for explaining a change in surface state due to ultraviolet irradiation through a photomask having a photocatalyst-containing layer.

FIG. 5 is a diagram showing an example of a conventional liquid crystal display device.

FIG. 6 is a diagram showing a liquid crystal display device disclosed in Japanese Patent Laid-Open No. 8-122824.

[Explanation of symbols]

101, 201 Base substrate 102, 202 Gate 103, 203 Gate insulating layer 104, 204 Amorphous silicon 105, 205 Drain 106, 206 Source 107, 207 Passivation layer 108, 208 Wetting change layer 109, 209 UV 110, 210 Photomask 111, 211 Photocatalyst-containing layer 112 Colored layer 212 Light-shielding layer, 313 Pixel electrode 402 Wettability change layer 403 UV light 404 Photomask 405 Photocatalyst-containing layer 501 TFT substrate 502 Color filter substrate 503 Liquid crystal layer 504 TFT glass substrate 505 Scan line 506 Signal line 507 Thin film transistor 508 Pixel electrode 509 Color filter 510 Black matrix 511 Overcoat layer 512 Counter electrode 513 Glass substrate 521 Gate insulator 525 Passivation film 530 Liquid crystal molecule 601 TFT substrate 602 Counter substrate 603 Liquid crystal layer 604 TFT glass substrate 605 Scan line 606 Signal line 607 thin film transistor 608 pixel electrode 609 color filter 611 overcoat layer 612 counter electrode 613 counter electrode Source electrode 620 gate electrode 621 gate insulating film 624 source electrode 625 a passivation film 626 a contact hole 630 a contact hole frame provided on the liquid crystal molecules 631 color filter

Continued front page    F-term (reference) 2H091 FA02Y FA34Y FC01 FC10                       FC18 FC25 FD04 FD05 GA03                       GA11 GA13 LA12 LA15                 2H092 JA23 JB00 JB51 KB26 MA16                       MA22 NA27 PA08 PA09                 5F110 AA16 BB01 CC07 DD02 GG02                       GG15 NN45 NN52 NN72 QQ01

Claims (6)

[Claims] 1. A first electrode substrate having a transparent common display electrode for pixel display formed on one surface of a transparent base substrate, and an active element made of a semiconductor thin film on each surface of the transparent base substrate for each pixel. Provided and arranged in a matrix,
And a second electrode substrate provided with a transparent pixel display electrode to which a voltage can be applied by an active element for each pixel,
The electrode substrate and the second electrode substrate are arranged so as to face each other with the common display electrode and the pixel display electrode facing the liquid crystal, and the liquid crystal between the pixel display electrode and the common electrode is a switching element. The active element selectively controls the transmitted light for each pixel by applying a voltage between the common display electrode of the first electrode substrate and the pixel display electrode of the second electrode substrate by the active element. A method for manufacturing an electrode substrate in a color liquid crystal display device, comprising a matrix type color liquid crystal display device, wherein a colored layer for color display is integrally provided on a second electrode substrate. Forming a colored layer of (a) providing a wettability changing layer having low wettability with respect to a material for forming the colored layer so as to include at least a region where the colored layer is provided; (B) Wet Selectively exposing the area part corresponding to the colored layer forming area of the sex change layer, and only the exposed area,
A color liquid crystal display device comprising: a selective exposure step of increasing wettability with respect to a material for forming a colored layer; and (c) a step of forming a colored layer in a region having an increased wettability. Manufacturing method of electrode substrate. 2. A first electrode substrate having a transparent common display electrode for pixel display formed on one surface of a transparent base substrate, and an active element made of a semiconductor thin film for each pixel on one surface of the transparent base substrate. Provided and arranged in a matrix,
And a second electrode substrate provided with a transparent pixel display electrode to which a voltage can be applied by an active element for each pixel.
The electrode substrate and the second electrode substrate are arranged so as to face each other with the common display electrode and the pixel display electrode facing the liquid crystal, and the liquid crystal between the pixel display electrode and the common electrode is a switching element. The active element controls the transmitted light for each pixel by selectively applying a voltage between the common display electrode of the first electrode substrate and the pixel display electrode of the second electrode substrate by the active element. A method of manufacturing an electrode substrate in a color liquid crystal display device, comprising: a matrix type color liquid crystal display device; and a second electrode substrate integrally provided with a light-shielding layer for color display. (A) a wettability changing layer forming step of providing a wettability changing layer having low wettability with a material for forming the light shielding layer so as to include at least a region where the light shielding layer is provided; (B) Wet Of a region corresponding to the light shielding layer formation region of the sex-change layer, and selectively exposed, only the exposed areas,
A color liquid crystal display device comprising: a selective exposure step of increasing wettability with respect to a material for forming a light-shielding layer; and (c) a step of forming a light-shielding layer in a region having high wettability. Manufacturing method of electrode substrate. 3. The method according to claim 1, further comprising a step of removing the wettability changing layer other than the portion where the colored layer and / or the light shielding layer is formed after the step of forming the colored layer and / or the light shielding layer. Of manufacturing an electrode substrate in a color liquid crystal display device of. 4. The material for forming a colored layer and / or a light-shielding layer only in an exposed region by performing selective exposure through a photomask having at least a photocatalyst-containing layer in the selective exposure step. The method for manufacturing an electrode substrate in a color liquid crystal display device according to claim 1, wherein the wettability is increased. 5. The method of manufacturing an electrode substrate in a color liquid crystal display device according to claim 1, wherein the step of forming the colored layer and / or the light shielding layer is an inkjet method. 6. The active matrix type color liquid crystal display device according to claim 1, wherein the active element is a TFT (Thin Film Transistor).
A method for manufacturing an electrode substrate in a color liquid crystal display device, comprising: