JPH09269481A - Production of color liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the adhesion property of an inorg. film and org. film when a protective film for protecting a color filter layer or its flattening layer from plasma is formed at the time of forming the film of ITO(indium tin oxide) by sputtering on this color filter layer or its flattening film by coating and firing type ceramics. SOLUTION: The coating and firing type ceramic film is formed between the color filter layer or the flattening film and a transparent driving electrode at the time of obtaining the transparent substrate constituted by forming the transparent driving electrode on the flattening film after the color filter layer and the flattening film consisting of the org. material are successively formed on a glass substrate. The ceramic precursors of the coating and firing type ceramic film are partly acted on the org. material of the flattening film at the time of forming the ceramic film described above, by which the inorg.-org. composite layer is formed at the boundary part.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a color liquid crystal display device, and more particularly, to a color liquid crystal display device having a protective film made of a coating and firing type ceramic between a color filter layer and a transparent driving electrode. The present invention relates to a manufacturing method.

[0002]

2. Description of the Related Art In a color liquid crystal display device, a first substrate having a color filter layer and a second substrate obtained through the same steps as the first substrate except that the color filter layer is not provided are provided with a spacer or a sealing material. Although it is composed of two elements facing each other, FIG. 3 illustrates the layer structure on the side of the first substrate having the color filter layer.

That is, on the side of the first substrate, first,
A color filter layer is provided on a transparent glass substrate, for example, STN (Super Twisted Ne).
Most of the color filter layers used for color display have irregularities of each pixel of RGB and the black matrix portion of 0.05 μm or more, regardless of the manufacturing method. A flattening film (layer) is formed on the layer.

Since this flattening film is usually made of an organic polymer material, a transparent conductive film (I) for forming drive electrodes is directly formed on the flattening film.
TO: indium tin oxide)
Problems such as deterioration of the flattening film occur during the film formation. Therefore, conventionally, a transparent conductive film is formed after forming a silica film on the flattening film by a sputtering method.

The presence of the silica film prevents the flattening film from being exposed to the plasma and deteriorating during the ITO sputtering film formation, and also improves the patterning accuracy of the ITO film. That is, when there is no silica film, side etching occurs due to poor adhesion between the resist and the flattening film during patterning, but the presence of the silica film reduces the side etching.

[0006]

By the way, although the film formation rate of silica is proportional to the sputter output, the sputter rate of silica is extremely slow, and therefore the sputter output must be increased in order to improve productivity. However, when the sputter output is increased, the flattening film is extremely deteriorated by the plasma at that time, and the reliability of the panel is impaired.
Of course, in order to prevent this, the sputter output can be reduced, but on the other hand, the productivity cannot be reduced.

Therefore, as a result of earnest studies, the present inventor has solved the above-mentioned conventional problems by using a coating and firing type ceramic film instead of the silica film by sputtering as a means for protecting the flattening film, thereby improving the productivity. However, the following concerns still remain.

That is, a ceramic film (inorganic polymer film)
Often has a small coefficient of thermal expansion, has a very high crosslink density, and tends to lack flexibility, so it is expected that the adhesion to the underlying planarizing film made of an organic material may not be sufficient, and cracks and Peeling may occur.

[0009]

The present invention has been made to further solve this problem. In Claim 1,
As shown in FIG. 1, a transparent substrate formed by sequentially forming a color filter layer and a planarizing film both made of an organic material on a glass substrate and then forming a transparent drive electrode on the planarizing film is used. In the method for manufacturing a color liquid crystal display device as a substrate, a coating and firing type ceramic film is formed between the flattening film and the transparent drive electrode, and a part of the ceramic precursor is formed during the formation of the coating and firing type ceramic film. To act on the organic substance of the planarizing film to form an inorganic-organic composite layer.

According to a second aspect of the present invention, as shown in FIG. 2, a color liquid crystal display device having a transparent substrate formed by sequentially forming a color filter layer and a transparent drive electrode on a glass substrate as one substrate. In the method for producing, a coating and firing type ceramic film is formed between the color filter layer and the transparent drive electrode, and at the time of forming the coating and firing type ceramic film, a part of the ceramic precursor is made into an organic substance of the color filter layer. To form an inorganic-organic composite layer.

The flattening film in claim 1 may be a commonly used organic polymer such as an epoxy acrylic type. Further, as in claim 2, the coating and firing type ceramic film can be directly formed on the color filter layer. In this case, the color filter layer is usually used in STN color liquid crystal display elements, for example, It may be formed by an electrodeposition method or a pigment dispersion type.

In any case, since the inorganic-organic composite layer is formed between the coating and firing type ceramic film and the underlying flattening film or color filter layer,
Sufficient adhesion is obtained between the two.

Further, as described in claim 3, it is preferable that the inorganic-organic composite layer in this case has a concentration gradient in which the content concentration of the inorganic component decreases as the depth of the organic substance increases. . In other words, the inorganic-organic composite layer is preferably a so-called inclined material having a concentration gradient in which the content of the inorganic component is higher on the organic surface side.

The following three methods are effective for forming an inorganic-organic composite layer having such a concentration gradient.
As a first method, as described in claim 4, an organic thin film is impregnated with a coating / firing type ceramic precursor, and they are simultaneously fired. According to this, although the ceramic precursor reaches the deep part of the organic film, a composite layer having a concentration gradient in which the concentration of the inorganic component is higher on the surface side of the organic film can be obtained.

As a second method, as described in claim 5, after coating and drying an organic thin film, a ceramic precursor is coated thereon and simultaneously baked and cured. According to this, since the ceramic precursor permeates deep into the organic matter in a state where the organic matter is not dense before curing, a composite layer having a concentration gradient in which the concentration of the inorganic component is higher on the surface side of the organic film is similar to the above. can get.

As a third method, as described in claim 6, a method of forming a porous thin film of an organic substance, applying a coating and firing type ceramic precursor, impregnating the inside of the porous substance and firing. Is. In this case, in order to make the organic film porous, for example, there is a method of curing the solvent without drying and removing the solvent after curing. In that case, the solvent may be removed by heating, but the solvent may be once replaced with a solvent having a low boiling point and then dried and volatilized.

In addition, as a device for efficiently providing a concentration gradient to the inorganic-organic composite layer, a method of appropriately increasing the diffusion rate of the ceramic precursor can be selected. For example, the molecular weight of the precursor can be reduced to reduce the organic substance. Various methods such as using a solvent having a polarity close to that of controlling the impregnation temperature and pressure can be exemplified.

Further, the coating and firing type ceramic precursor does not necessarily have to be a special one, and preferably, as described in claim 7, perhydrosilazane,
Alternatively, a metal alkoxide or a partial hydrolyzate thereof can be mentioned.

That is, the metal alkoxides are represented by the general formula: MR _n (OR) _4-n (where M is a metal atom, R is an alkyl group, and n is an integer of 0 or 1 to 3, respectively). And the partial hydrolyzate thereof can be used.

In summary, the conditions required in the present invention are:
A dense film is formed by low-temperature baking, and the low-temperature baking temperature is a temperature at which the planarizing film made of an organic polymer or the color filter layer is not thermally decomposed.
The temperature is 00 ° C or lower, preferably 270 ° C or lower. Perhydropolysilazane, silicon tetramethoxide, or a derivative thereof is suitable as a material capable of realizing film formation at such a temperature.

The ceramic precursor may be partially organically modified. However, if the degree of organic modification is too large, deterioration may occur during ITO sputtering, but if it is an appropriate amount, good compatibility with organic matter can be expected. As the method of organic modification,
A method of reacting a metal alkoxide with a series of organic silane compounds generally known as a silane coupling agent can be exemplified.

A transparent conductive film (ITO film) is formed on the ceramic film formed as described above by a sputtering method and patterned to form a drive electrode (FIGS. 1 and 2).
reference). In order to obtain a color liquid crystal display device, two substrates with drive electrodes that have been subjected to an alignment treatment (though,
One of them does not have a color filter layer) is prepared, spacers are sprinkled on one of them, a sealing material is provided on the other substrate, and both substrates are opposed to each other and pressure-bonded,
Create an empty cell.

After injecting liquid crystal into the empty cell to form a liquid crystal cell, a polarizing plate, a reflection plate, a retardation plate, a touch panel, a light source and the like are combined as necessary to obtain a desired color liquid crystal display. The device is obtained.

[0024]

【Example】

<< Example 1 >> An acrylic epoxy-based planarizing agent JSS-715 is formed on the electrodeposition type color filter layer on the glass substrate.
(Manufactured by Japan Synthetic Rubber Co., Ltd.) was applied by a spin coating method so that the thickness after firing was 2 μm, and dried at 100 ° C. for 10 minutes. Next, perhydroxysilazane NL-11
0 (xylene solution containing 10% solid content, manufactured by Tonensha Co., Ltd.) was spin-coated and baked at 250 ° C. for 1 hour. The film thickness at this time was 0.12 μm. Subsequently, the ITO film was patterned by a usual method to form a transparent drive electrode. The size of the side etch at this time is 0.8 to 1.2.
At the micron level, it was comparable to the conventional silica film produced by the sputtering method, and the effect of preventing side etching was confirmed. When a color liquid crystal display panel was produced by combining the substrate thus obtained and a counter substrate having no color filter layer by a usual method, no defective phenomenon was observed even after various reliability tests.

Example 2 A pigment-dispersed color filter layer having a thickness of about 1.6 μm was formed on a glass substrate, and MS51SG1 (methyl silicate hydrolyzate, methanol solution, Mitsubishi Chemical Co. Made) 15%
The glass substrate was dipped in the solution for 10 minutes and gently pulled up. Then, after drying at 100 ° C for 5 minutes, 270 ° C
When it was cured in the furnace, a ceramic film having a thickness of about 1.2 μm was obtained, and its flatness was ± 0.07 μm. Hereinafter, a color liquid crystal display panel was prepared in the same manner as in Example 1 and various reliability tests were conducted, but no defective phenomenon was observed, and the effect of the inorganic-organic composite layer (gradient material) was recognized.

Comparative Example 1 A pigment-dispersed color filter layer is formed on a glass substrate, and an acrylic epoxy resin-based leveling agent JSS-715 is formed on the color filter layer.
(Manufactured by Japan Synthetic Rubber Co., Ltd.) was applied by a spin coating method and baked at 250 ° C. to form a flattening film of about 2 μm.
Next, perhydroxysilazane NL-110 (solid content 1
A 0% solution of xylene, manufactured by Tonensha Co., Ltd.) was applied by spin coating and baked at 250 ° C. for 1 hour. The film thickness at this time was 0.12 μm. Hereinafter, a color liquid crystal display panel was produced in the same manner as in Example 1, but a high temperature and high humidity standing test (60 ° C., relative humidity 90%, standing time 1000 hours)
After the completion, it was confirmed that cracks were formed on the ITO, which are thought to be due to insufficient adhesion.

[0027]

As described above, according to the present invention,
To form a coating and firing type ceramic film on the color filter layer or its flattening film to protect them from plasma during sputtering of ITO,
By allowing a part of the ceramic precursor to act on the organic material of the color filter layer or the flattening film to form the inorganic-organic composite layer, sufficient adhesion can be obtained between the inorganic film and the organic film. Therefore, it is possible to provide a highly reliable color liquid crystal display device with improved productivity.

[Brief description of drawings]

FIG. 1 is a schematic diagram for explaining a layer structure of a color liquid crystal display device according to a first embodiment of the present invention.

FIG. 2 is a schematic diagram for explaining a layer structure of a color liquid crystal display device according to a second embodiment of the present invention.

FIG. 3 is a schematic view similar to FIGS. 1 and 2 for explaining a layer structure of a color liquid crystal display element as a conventional example.

Claims (7)

[Claims] 1. A color liquid crystal display having a transparent substrate formed by sequentially forming a color filter layer and an organic planarizing film on a glass substrate and then forming a transparent drive electrode on the planarizing film as one substrate. In the device manufacturing method, a coating and firing type ceramic film is formed between the flattening film and the transparent drive electrode, and at the time of forming the coating and firing type ceramic film, a part of the ceramic precursor is formed into the flattening film. A method for producing a color liquid crystal display device, which comprises reacting an organic substance to form an inorganic-organic composite layer. 2. A method of manufacturing a color liquid crystal display device, comprising a transparent substrate, which is formed by sequentially forming a color filter layer and a transparent drive electrode on a glass substrate, as one substrate.
A coating and firing type ceramic film is formed between the color filter layer and the transparent drive electrode, and at the time of forming the coating and firing type ceramic film, a part of the ceramic precursor is allowed to act on the organic substance of the color filter layer, Inorganic-
A method for manufacturing a color liquid crystal display device, which comprises forming an organic composite layer. 3. The color liquid crystal according to claim 1, wherein the inorganic-organic composite layer has a concentration gradient in which the concentration of the inorganic component decreases as the depth of the organic substance increases. Display element manufacturing method. 4. In forming the inorganic-organic composite layer, the organic thin film is impregnated with a part of the coating and firing type ceramic precursor, and they are fired at the same time. 4. The method for manufacturing a color liquid crystal display element according to any one of 3 above. 5. In forming the inorganic-organic composite layer, the organic thin film is coated and dried, and then the coating and firing type ceramic precursor is coated thereon, and they are simultaneously fired. A method for manufacturing a color liquid crystal display device according to claim 1. 6. In forming the inorganic-organic composite layer, the organic substance is formed into a porous thin film, the coating and firing type ceramic precursor is applied, and a part thereof is impregnated into the porous body and fired. 4. The method for manufacturing a color liquid crystal display element according to claim 1, wherein 7. The color liquid crystal display device according to claim 1, wherein the coating / firing type ceramic precursor is perhydrosilazane, a metal alkoxide, or a partial hydrolyzate thereof. Manufacturing method.