JPH08286030A - Color filter substrate and color liquid crystal display device using the same - Google Patents

Abstract

PURPOSE: To obtain a color filter substrate used for a color liquid crystal display device which exhibit excellent display quality and has high reliability even in a high temp. and high humidity atmosphere by forming a silane surface- treating agent layer on the first transparent electrically conductive layer. CONSTITUTION: This color filter substrate 1 is obtained by forming a color filter layer 5 consisting of a black matrix 6 and a colored layer 7 on the first transparent conductive layer 3 which is placed on an insulating transparent substrate 2 and used for the electrodeposition, through a silane surface-treating agent layer 4. Further, the second transparent conductive layer 8 for driving the liquid crystal is formed on the color filter layer 5. The layer 4 is a transparent thin layer formed by using a silane coupling agent or surface modifier. As the silane coupling agent, a vinyl silane compound, acrylic silane compound or the like is used. As the surface modifier, a chlorosilane, alkoxysilane or the like is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter substrate and a color liquid crystal display device, and more particularly to a color liquid crystal display device having excellent display quality and high reliability, and a color filter substrate used for the same.

[0002]

2. Description of the Related Art In recent years, a color liquid crystal display device has been attracting attention as a flat display. Generally, a color liquid crystal display device includes a color filter substrate having a black matrix and a plurality of colors (usually, three primary colors of red (R), green (G), and blue (B)) and a counter electrode substrate. It has a structure in which a liquid crystal layer is sandwiched between. Then, a color image is obtained by controlling the light transmittance of the liquid crystal layer in the portion corresponding to each pixel of the colored layers R, G, B of each color. Therefore, the color filter substrate is essential for the color liquid crystal display device, and is an important member that affects the display quality itself of the color liquid crystal display device.

Conventionally, for the black matrix and the coloring layer of the color filter substrate, a dyeing method is applied in which a dyeing base material is applied, and a pattern formed by exposing and developing through a photomask is dyed. , A pigment dispersion method of exposing and developing through a photomask,
Further, it is formed by a printing method or the like in which each color is printed with printing ink. In recent years, the manufacturing cost is lower, and
There is a demand for high-performance color filter substrates, and in order to meet such demands, the use efficiency of the paint is high and the formation time of the black matrix and the coloring layer is short (tens of seconds).
Attention is focused on color filter substrates manufactured by the electrodeposition method, which has excellent production capacity.

In the above electrodeposition method, a transparent conductive layer for electrodeposition is formed on a transparent substrate, a positive resist layer is formed on the transparent conductive layer, and exposure is performed through a mask having a predetermined pattern. Then, the exposed portion is dissolved and removed to expose a predetermined portion of the transparent conductive layer, and then, while the transparent substrate is immersed in an electrodeposition liquid of a predetermined color, electricity is applied from the transparent conductive layer around the transparent substrate to energize it. Then, the black matrix and the coloring layer are sequentially provided to form the color filter layer by repeating such electrodeposition operation. After the color filter layer including the black matrix and the colored layer is formed in this way, the entire surface of the substrate is irradiated with ultraviolet rays to remove the positive resist layer, and then the liquid crystal layer is driven on the color filter layer. Forming a transparent conductive layer of
Polyimide is applied as an alignment layer, baked, and then subjected to alignment treatment (rubbing) to obtain a color filter substrate.

A method of manufacturing a color filter substrate using the above electrodeposition method has hitherto been disclosed in, for example, Japanese Patent Laid-Open No. 61-20.
3403, JP-A-61-270701, and the like.

[0006]

In the color filter substrate manufactured by the electrodeposition method as described above, the color filter layer including the black matrix and the coloring layer is formed on the transparent conductive layer for electrodeposition. However, the adhesive force between the transparent conductive layer and the color filter layer is the adhesion between the color filter layer and the transparent substrate which are directly formed on a transparent substrate such as a conventional glass substrate by a dyeing method, a pigment dispersion method, a printing method or the like. There is a problem that it is inferior to strength. The causes of the low adhesion of the color filter layer in the electrodeposition method are considered as follows. The transparent conductive layer is formed of a metal oxide such as indium tin oxide (ITO).
The surface tension of metal oxides such as O is much higher than the surface tension of transparent substrates such as glass substrates. Therefore, when an electrodeposition film (color filter layer) having a relatively small surface tension such as a black matrix or a colored layer using a polymer compound as a vehicle is formed on a metal oxide such as ITO, the wettability of both Will be extremely bad. Furthermore, the surface hydroxyl groups of metal oxides such as ITO are less than that of glass substrates,
Therefore, the hydrogen bond existing between the color filter layer and the metal oxide such as ITO is smaller than the hydrogen bond existing between the color filter layer and the glass substrate.

If the adhesive force between the transparent conductive layer and the color filter layer is not sufficient as described above, in a color liquid crystal display device manufactured by sealing the liquid crystal layer between the color filter substrate and the counter electrode substrate, There is a problem that the color filter layer is peeled off when left in a high humidity atmosphere for a long time, the image quality is deteriorated, and it is difficult to drive the color liquid crystal display device accurately.

The problem of the low adhesion of the color filter layer in the above electrodeposition method is that the transparent conductive layer for electrodeposition is previously patterned and the color filter layer is formed only on this transparent power transmission layer ( JP-A-59-114572
No.) is a similar problem.

The present invention has been made in view of the above circumstances, and has a highly reliable color liquid crystal display device which exhibits excellent display quality even in a high temperature and high humidity atmosphere, and this color liquid crystal display. An object is to provide a color filter substrate used in an apparatus.

[0010]

In order to achieve such an object, the color filter substrate of the present invention comprises an insulative transparent substrate and a first transparent conductive layer sequentially laminated on the transparent substrate. The silane-based surface treatment agent layer, the color filter layer, and the second transparent conductive layer were provided.

In the color filter substrate of the present invention, the first transparent conductive layer is provided only in the area where the color filter layer is formed, and the silane-based surface treatment agent layer is formed with the first transparent conductive layer. Which is not formed on the transparent substrate and the first transparent conductive layer, or the first transparent conductive layer is provided only in the formation region of the color filter layer, and the silane-based surface treatment is performed. The agent layer was formed only on the first transparent conductive layer, and a protective film was provided between the color filter layer and the second transparent conductive layer.

The color liquid crystal display device of the present invention is a color liquid crystal display device having a color filter substrate and a counter electrode substrate facing each other, and a liquid crystal layer sealed between the both substrates, wherein the color filter substrate is The color filter substrate is any one of the above.

[0013]

The first transparent conductive layer for electrodeposition formed on the insulating transparent substrate has a large surface tension and a small number of functional groups on the surface. However, a silane-based surface treatment agent is added to the first transparent conductive layer. By forming a layer, it is possible to form a surface having a low surface tension and an increased surface functional group, whereby the color filter layer having a low surface tension formed on the above silane-based surface treatment agent layer can be formed. , The wettability with the silane-based surface treatment agent layer is high, and a hydrogen bond or a covalent bond is generated between the surface functional group of the silane-based surface treatment agent layer, so that the silane-based surface treatment agent layer has It is held on the transparent conductive layer 1 with a sufficient adhesive force.

[0014]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic diagram showing an example of the color filter substrate of the present invention. In FIG. 1, a color filter substrate 1 of the present invention is colored with a black matrix 6 via a silane-based surface treatment agent layer 4 on a first transparent conductive layer 3 for electrodeposition provided on an insulating transparent substrate 2. A color filter layer 5 including a layer 7 is formed, and a second transparent conductive layer 8 for driving a liquid crystal is further formed on the color filter layer 5.
Are formed.

An insulative transparent substrate 2 constituting such a color filter substrate 1 is an inflexible rigid material such as quartz glass, Pyrex glass, or synthetic quartz plate.
Alternatively, a flexible material having flexibility such as a transparent resin film or an optical resin plate can be used. Among them, 7059 glass manufactured by Corning Co., Ltd. is a material having a small coefficient of thermal expansion, is excellent in dimensional stability and workability in high temperature heat treatment, and is a non-alkali glass containing no alkali component in the glass. It is suitable for a color filter substrate used in a color liquid crystal display device for LCD according to the method.

The first transparent conductive layer 3 and the second transparent conductive layer 8 constituting the color filter substrate 1 are made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and The alloy or the like is used to form the film by a general film forming method such as a sputtering method, a vacuum vapor deposition method, or a CVD method. The thickness of the first transparent conductive layer 3 for electrodeposition is about 90 to 190 nm, preferably 100.
˜175 nm, and the thickness of the second transparent conductive layer 8 for driving liquid crystal is about 20 to 200 nm,
Preferably, it can be about 90 to 190 nm.

Further, the silane-based surface treatment agent layer 4 described above.
Is a transparent thin layer formed by using a silane coupling agent or a surface modifier as described below.

Examples of the silane coupling agent for forming the silane-based surface treatment agent layer 4 include vinylsilane, acrylsilane, epoxysilane, aminosilane and the like. More specifically, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and the like can be used as the vinylsilane.

Examples of acrylsilanes include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane.

As the epoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
Examples thereof include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldietoxylan.

Further, as aminosilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethylditrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Etc. can be used. As other silane coupling agents, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane,
γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane and the like can be used.

On the other hand, as the surface modifier for forming the silane-based surface treatment agent layer 4, chlorosilane, alkoxysilane, silazane or the like can be used. Specifically, as chlorosilane, methyltrichlorosilane,
Methyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, trimethylchlorosilane, dimethylvinylchlorosilane, methylvinyldichlorosilane, methylchlorodisilane, phenyltrichlorosilane, triphenylchlorosilane, methyldiphenylchlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, chloromethyl Dimethylchlorosilane or the like can be used.

As the alkoxysilane, trimethylmethoxysilane, trimethylethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethylethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane. , Tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinylmethoxysilane, Methylvinyldiethoxysilane or the like can be used. As the silazane, hexamethyldisilazane, a cyclic silazane mixture,
N, N'-bis (trimethylsilyl) urea, N-trimethylsilylacetamide, dimethyltrimethylsilylamine, diethyltrimethylsilylamine, trimethylsilylimidazole, N-trimethylsilylphenylurea and the like can be used.

The silane-based surface treatment agent layer 4 is formed by a known coating means such as a spin coater, a roll coater, a dip coater or a spray coater, using the silane coupling agent or the surface modifier described above. However, it is particularly preferable to use a silane coupling agent. The thickness of the silane-based surface treatment agent layer 4 is not particularly limited, but if the silane-based surface treatment agent layer is several μm or more, not only the adhesive strength between the transparent conductive layer and the color filter layer is lowered, but also the color filter It lowers the curability of the layer and significantly reduces the transmittance of the colored layer. Therefore, it is preferable that the silane-based surface treatment agent is uniformly present as a monomolecular layer between the transparent conductive layer and the color filter layer.

The colored layer 7 which constitutes the color filter layer 5 of the color filter substrate 1 has a desired pattern such as a red pattern 7R, a green pattern 7G and a blue pattern 7B such as a mosaic type, a stripe type, a triangle type and a four pixel arrangement type. The black matrixes 6 are arranged and provided between the colored patterns and outside the colored layer 7 forming region.

In the above-mentioned color filter substrate of the present invention, the first transparent conductive layer 3 for electrodeposition is formed on the entire surface of the transparent substrate 2, but in the color filter substrate of the present invention,
The transparent conductive layer 3 may be provided only in a predetermined portion of the area where the color filter layer 5 is formed. An example of such a color filter substrate of the present invention will be described with reference to FIGS.

First, the color filter substrate 1 of the present invention shown in FIG. 2 is the first transparent conductive film for electrodeposition provided in a region corresponding to the formation region of the color filter layer 5 on the insulating transparent substrate 2. Layer 3, transparent conductive layer 3 and silane-based surface treatment agent layer 4 formed on transparent substrate 2 on which transparent conductive layer 3 is not formed, and transparent conductive layer 3 via silane-based surface treatment agent layer 4 Black matrix 6 provided above
A color filter layer 5 including a colored layer 7 is formed, and a second transparent conductive layer 8 for driving a liquid crystal is formed on the color filter layer 5. Further, as shown in FIG. 3, the silane-based surface treatment agent layer 4 is added to the first transparent conductive layer 3
It may be formed only on the top.

Further, in the color filter substrate 1 of the present invention shown in FIG. 4, the first transparent conductive layer 3 provided on the insulating transparent substrate 2 is formed on the colored layer 7 in the formation region of the color filter layer 5. The silane-based surface treatment agent layer 4 is provided on the transparent substrate 2 which is formed only in the corresponding region and on which the first transparent conductive layer 3 for electrodeposition and the transparent conductive layer 3 are not formed. Furthermore, as shown in FIG. 5, the silane-based surface treatment agent layer 4 may be formed only on the first transparent conductive layer 3.

Further, the color filter substrate of the present invention is
A protective film may be provided between the color filter layer 5 including the black matrix 6 and the colored layer 7 and the second transparent conductive layer 8 for driving the liquid crystal. FIG. 6 is a schematic configuration diagram showing an example in which a protective film 9 is provided between the color filter layer 5 and the second transparent conductive layer 8 in the color filter substrate 1 of the present invention shown in FIG. Such a protective film 9 can be formed using, for example, a thermosetting polymer material such as an acrylic resin, an epoxy resin, a urethane resin or an ultraviolet curable polymer material. The thickness of the protective film 9 is 0.2
The thickness can be about 10 to 10 μm, preferably about 0.5 to 5 μm. In addition, also in the color filter substrate of another aspect of the present invention shown in FIGS. 2 to 5, the protective layer can be provided between the color filter layer 5 and the second transparent conductive layer 8 for driving liquid crystal. Of course.

Next, a method for manufacturing the color filter substrate of the present invention will be described by taking the color filter substrate 1 shown in FIG. 1 as an example.

First, the transparent conductive layer 3 is formed of a transparent conductive material such as indium tin oxide (ITO) on the entire surface of the multi-faced insulating transparent substrate 2 (FIG. 7A).

Next, the silane-based surface treatment agent layer 4 is formed on the transparent conductive layer 3 (FIG. 7 (B)). The silane-based surface treatment agent layer 4 is formed by using a spin coater, a roll coater,
It can be performed by a known coating means such as a dip coater or a spray coater. As shown in FIG. 5 described above, the silane-based surface treatment agent layer 4 is formed only on the first transparent conductive layer 3 formed in a portion corresponding to the formation region of the colored layer 7.
When providing a silane-based surface treatment agent layer 4 at this stage
Is not formed, and the silane-based surface treatment agent layer 4 is provided for each development of the resist layer described below.

Thereafter, a photoresist is applied on the silane-based surface treatment agent layer 4 to form a resist layer 10, and the resist layer 10 is exposed through a photomask 11 corresponding to a desired pattern, for example, a black matrix pattern. (FIG. 7C). Then, the transparent conductive layer 3 is exposed to a shape corresponding to the black matrix pattern by developing and drying, and the transparent substrate 2 is immersed in an electrodeposition bath in which a black pigment is dispersed, and a voltage is applied to the transparent conductive layer 3. A black electrodeposition material is deposited by applying, washed thoroughly with water, and then dried to form a pinhole-free black matrix 6 (FIG. 7).
(D)).

Similarly, the red pattern 7R, the green pattern 7G and the blue pattern 7B are formed to form the color filter layer 5 (FIG. 7 (E)).

The electrodeposition material used in the above steps is generally made of an organic material (polymer material), and its original form is well known as an electrodeposition coating method. In electrodeposition coating,
There are cation electrodeposition and anion electrodeposition due to electrochemical reaction with the main electrode. This is classified according to whether the electrodeposited material exists as a cation or behaves as an anion.
Examples of the organic polymer substance used for electrodeposition include various organic polymer substances such as natural fats and oils, synthetic fats and oils, alkyd resins, polyester resins, acrylic resins and epoxy resins.

In the anion type, maleated oil and polybutadiene resin have been known for a long time, and the curing of the electrodeposition material is based on the oxidative polymerization reaction. The cation type is mostly an epoxy resin and can be used alone or modified. Other,
So-called polyamino resins such as melamine resins and acrylic resins are often used, and a strong colored layer can be formed by thermosetting, photocuring or the like.

In electrodeposition in the production of a color filter substrate, finely pulverized pigments or dyes are dispersed in an anion type or cation type electrodeposition bath and co-deposited with the ionic polymer material on the conductive part.

Then, a second transparent conductive layer 8 is formed so as to cover the color filter layer 5 composed of the black matrix 6 and the colored layer 7 (FIG. 7 (F)). This transparent conductive layer 8
Is a general film forming method such as a sputtering method, a vacuum vapor deposition method, a CVD method, etc., using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and their alloys as described above. Can be formed by.

Next, the color liquid crystal display device of the present invention will be described. The color liquid crystal display device of the present invention is one in which a liquid crystal layer is sealed between the color filter substrate and the counter electrode substrate as described above.

FIG. 8 is a partial sectional view showing an example of such a color liquid crystal display device of the present invention. In FIG.
In the color liquid crystal display device 21 of the present invention, the color filter substrate 1 of the present invention and the counter electrode substrate 23 of the present invention as described above are opposed to each other at a predetermined interval, the peripheral portion is sealed by a seal member 24, and a space between both substrates is provided. The liquid crystal layer 25 having a thickness of about 5 to 10 μm is formed. Polarizing plates 26 and 27 are provided outside the color filter substrate 1 and the counter electrode substrate 23, respectively. In addition, the liquid crystal layer 2 of the color filter substrate 1
An alignment layer 29 is provided on the surface in contact with 5.

The counter electrode substrate 23 constituting the color liquid crystal display device 21 is provided with a transparent electrode 32 for driving liquid crystal and a thin film transistor (TFT) 33 on a transparent substrate 31, and an alignment layer 34 so as to cover the transparent electrode 32. Are formed. On the counter electrode substrate 23, a group of gate lines (not shown) for opening and closing the thin film transistors (TFTs) 33, a group of signal lines (not shown) for supplying a video signal, and a take-out portion of a corner on the color filter substrate side. A voltage supply line is provided to the color filter electrode that has been transferred from (transferred (provided to one to three take-out parts depending on the design)). These leads 35 are typically
The thin film transistor (TFT) 33 is made of a metal such as Al and is formed collectively in the manufacturing process. The thin film transistor (TFT) 33 is connected to the transparent electrode 32 and is also connected to an electrical connection line 42 from an external drive IC 41. ing. In addition, on the surface of the counter electrode substrate 23 in contact with the liquid crystal layer 25, the alignment layer 34 is formed.
Is provided.

Alignment layer 29 provided on the color filter substrate 1 and alignment layer 3 provided on the counter electrode substrate 23.
Reference numeral 4 is a layer containing at least one of polyimide-based, polyamide-based, polyurethane-based and polyurea-based organic compounds, and has a thickness of 0.01 to 1 μm, preferably about 0.03 to 0.5 μm. Can be Such alignment layers 29 and 34 are applied by a known application method such as various printing methods and then baked and then subjected to an alignment treatment (rubbing).

In this color liquid crystal display device 21, each colored pattern 7R, 7G, 7B of the color filter substrate 1 constitutes a pixel, and the liquid crystal driving device corresponding to each pixel is illuminated with illumination light from the polarizing plate 27 side. The liquid crystal layer 25 operates as a shutter by turning on and off the transparent electrode of, and each pixel of the colored patterns 7R, 7G, and 7B transmits light to perform color display. By using the above-described color filter substrate 1 of the present invention, such a color liquid crystal display device 21 exhibits excellent display quality even in an environment of high temperature and high humidity and becomes highly reliable.

In the above embodiment, the driving method is TFT
Although the active matrix system is used, the color liquid crystal display device of the present invention is not limited to this.
For example, methods such as simple matrix and segment, MI
Needless to say, an active matrix method using a two-terminal element such as M (metal / insulator / metal) may be used.

Next, the present invention will be described in more detail with reference to more specific examples. (Example 1) Indium tin oxide (IT) was formed on a glass substrate (Corning 7070) having a thickness of 1.1 mm.
O) is formed into a film by the sputtering method, and the first electrodeposition is performed.
ITO transparent conductive layer (thickness 113 nm, sheet resistance 13
Ω / SQ) was formed.

Next, an aminosilane coupling agent (KBM manufactured by Shin-Etsu Chemical Co., Ltd.) was formed on the ITO transparent conductive layer.
A 0.5% ethyl cellosolve acetate solution of 602) was applied by a spin coating method and then dried at 120 ° C. for 30 minutes to form a silane-based surface treatment agent layer.

Then, a photosensitive resist (Tokyo Ohka Kogyo Co., Ltd.) was formed on the silane-based surface treatment agent layer formed as described above.
OFPR-800) was applied by spin coating to form a resist layer (thickness 2.5 μm). The resist layer was exposed through a photomask having a black matrix pattern. This exposure was carried out by irradiating with 70 mJ / cm ² of ultraviolet rays using an ultraviolet exposure device (JL3300 manufactured by Oak Manufacturing Co., Ltd.) having an ultrahigh pressure mercury lamp. Next, the exposed portion was developed and removed to form a resist layer having a black matrix pattern.

Then, the ITO transparent conductive layer was used as an anode in an electrodeposition liquid for black matrix having the following composition,
Using a platinum electrode as a cathode, a glass substrate was immersed so that the electrode interval was 50 mm, and the electrodeposition was performed by energizing at a DC voltage of 28 V and 25 ° C. for 20 seconds. Next, the glass substrate taken out from the electrodeposition liquid was thoroughly washed with water and then dried at 80 ° C. for 10 minutes to form a black matrix.

(Electrodeposition solution for black matrix) Acrylic resin 750.0 parts by weight (Toa Gosei Chemical Co., Ltd. Aron S-4030) Melamine resin (Sumitomo Chemical Co., Ltd. M-66B) 250.0 parts by weight Triethylamine 61.8 parts by weight carbon black 333.0 parts by weight deionized water 11935.2 parts by weight Next, the unexposed part of the resist layer was exposed through a photomask having a pattern for a red pattern. This exposure was performed by irradiating ultraviolet rays of 100 mJ / cm ² using an ultraviolet exposure device (JL3300 manufactured by Oak Manufacturing Co., Ltd.) having an ultrahigh pressure mercury lamp. next,
The exposed part is developed and removed, and I
The TO transparent conductive layer was exposed.

Next, electrodeposition was carried out in the same manner as black matrix formation, using the ITO transparent conductive layer as an anode and the platinum electrode as a cathode in a red pattern electrodeposition solution having the following composition. Next, the glass substrate taken out from the electrodeposition liquid was thoroughly washed with water and then dried at 80 ° C. for 10 minutes to form a red pattern layer having good transparency.

(Electrodepositing solution for red pattern) Acrylic resin 750.0 parts by weight (Toa Gosei Chemical Co., Ltd. Aron S-4030) Melamine resin (Sumitomo Chemical Co., Ltd. M-66B) 250.0 parts by weight Triethylamine 61.8 parts by weight Pigment Red 48S (manufactured by Sanyo Industry Co., Ltd.) 500.0 parts by weight Deionized water 13438.2 parts by weight Further, the unexposed part of the resist layer is a photomask having a pattern for a green pattern. Through the same procedure, exposure was performed in the same manner as in the formation of the red pattern, and then the exposed portion was developed and removed, and the ITO transparent conductive layer was exposed in the pattern for the green pattern.

Then, a red pigment (Pigment Red 48
An electrodeposition solution for a green pattern was prepared in the same manner as the electrodeposition solution for the red pattern layer except that a green pigment (phthalocyanine green) was used instead of S). Then, in the green pattern electrodeposition liquid, the ITO transparent conductive layer as an anode,
Using a platinum electrode as a cathode, the substrate was dipped so that the electrode interval was 50 mm, and the electrodeposition was performed by energizing at a DC voltage of 30 V and 25 ° C for 20 seconds. Next, the glass substrate taken out from the electrodeposition liquid was thoroughly washed with water and then dried at 80 ° C. for 10 minutes to form a green pattern layer having good transparency.

Further, the unexposed portion of the resist layer is
Through a photomask having a pattern for a blue pattern, exposure is performed as in the case of forming a red pattern, and then,
The exposed part is developed and removed, and I
The TO transparent conductive layer was exposed.

Then, a red pigment (Pigment Red 48
An electrodeposition solution for blue pattern was prepared in the same manner as the above-mentioned electrodeposition solution for red pattern layer except that a blue pigment (phthalocyanine blue) was used instead of S). Then, the ITO transparent conductive layer was used as an anode and the platinum electrode was used as a cathode in the electrodeposition liquid for blue pattern, the substrate was dipped so that the electrode interval was 80 mm, and electricity was applied for 20 seconds at a DC voltage of 30 V and 25 ° C. I put on my clothes. Next, the glass substrate taken out from the electrodeposition solution was thoroughly washed with water and then dried at 80 ° C. for 10 minutes to form a blue pattern layer having good transparency.

Then, 200 mJ / cm ² of ultraviolet rays were irradiated, and the remaining resist layer was developed and peeled off. As a result, a color filter layer having a black matrix, a red pattern, a green pattern and a blue pattern was formed. Then, it was cured at 200 ° C. for 1 hour to obtain a color filter substrate.

The color filter substrate thus obtained was immersed in boiling water for 1 hour and a tape peeling test was conducted before and after the immersion. As a result, there was no color filter layer that fell off before and after immersion, and the color filter layer was silane. It was confirmed that it was held with high adhesiveness on the ITO transparent conductive layer through the system surface treatment agent layer. (Example 2) As in Example 1, ITO was formed on the glass substrate.
A transparent conductive layer is formed, and a vinyl silane coupling agent (KBM manufactured by Shin-Etsu Chemical Co., Ltd.) is formed on the ITO transparent conductive layer.
A 0.5% ethyl cellosolve acetate solution of 1003) was applied by a spin coating method, and then dried at 120 ° C. for 30 minutes to form a silane-based surface treatment agent layer.

After that, a color filter substrate was manufactured in the same manner as in Example 1. The color filter substrate was evaluated in the same manner as in Example 1. As a result, there was no color filter layer that fell off before and after immersion, and the color filter layer had high adhesion to the ITO transparent conductive layer through the silane-based surface treatment agent layer. It was confirmed that it was retained by sex. (Example 3) Similar to Example 1, ITO was formed on the glass substrate.
A transparent conductive layer is formed, and a 0.5% ethyl cellosolve acetate solution of a surface modifier hexamethyldisilazane (SZ6079 manufactured by Toray Silicone Co., Ltd.) is applied on the ITO transparent conductive layer by spin coating. Then 12
It was dried at 0 ° C. for 30 minutes to form a silane-based surface treatment agent layer.

After that, a color filter substrate was manufactured in the same manner as in Example 1. The color filter substrate was evaluated in the same manner as in Example 1. As a result, there was no color filter layer that fell off before and after immersion, and the color filter layer had high adhesion to the ITO transparent conductive layer through the silane-based surface treatment agent layer. It was confirmed that it was retained by sex. (Comparative Example) Except that a silane-based surface treatment agent layer is not formed on the ITO transparent conductive layer provided on the glass substrate,
A color filter substrate was produced in the same manner as in the above example. A tape peeling test before and after immersion was performed on this color filter substrate in the same manner as in the example. As a result, good adhesion was observed between the color filter layer and the ITO transparent conductive layer before the immersion, but after the immersion, the color filter layer peeled off and could not be used as a color filter substrate. there were.

[0060]

As described above in detail, according to the present invention, the first transparent conductive layer for electrodeposition formed on the insulating transparent substrate has a large surface tension and a small number of functional groups on the surface. ,
By forming a color filter layer on the first transparent conductive layer via a silane-based surface treatment agent layer, the color filter layer having a low surface tension exhibits high wettability with the silane-based surface treatment agent layer. In addition, hydrogen bonds or covalent bonds are generated between the surface functional groups of the silane-based surface treatment agent layer, and the silane-based surface treatment agent layer holds the first transparent conductive layer with sufficient adhesive force. The color filter substrate and the counter electrode substrate thus configured are opposed to each other, and the liquid crystal layer is sealed between the two substrates to form a color liquid crystal display device, so that it can be left in a high temperature and high humidity atmosphere. It is possible to provide a highly reliable color liquid crystal display device that stably exhibits excellent display quality, can be accurately driven.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an example of a color filter substrate of the present invention.

FIG. 2 is a schematic configuration diagram showing another example of the color filter substrate of the present invention.

FIG. 3 is a schematic configuration diagram showing another example of the color filter substrate of the present invention.

FIG. 4 is a schematic configuration diagram showing another example of the color filter substrate of the present invention.

FIG. 5 is a schematic configuration diagram showing another example of the color filter substrate of the present invention.

FIG. 6 is a schematic configuration diagram showing another example of the color filter substrate of the present invention.

FIG. 7 is a drawing for explaining the manufacturing method of the color filter substrate of the present invention.

FIG. 8 is a partial cross-sectional view showing an example of a color liquid crystal display device of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Color filter substrate 2 ... Transparent substrate 3 ... First transparent conductive layer 4 ... Silane-based surface treatment agent layer 5 ... Color filter layer 6 ... Black matrix 7 ... Coloring layer 8 ... Second transparent conductive layer 9 ... Protective film 21 ... Color liquid crystal display device 23 ... Counter electrode substrate 25 ... Liquid crystal layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Norikatsu Ono 1-1-1, Ichigayaka-cho, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd. (72) Inventor Hiroyoshi Omiga Higashi Shinohara, Kohoku-ku, Yokohama 3-chome 20-17

Claims (5)

[Claims] 1. An insulating transparent substrate, and a first transparent conductive layer, a silane-based surface treatment agent layer, a color filter layer, and a second transparent conductive layer, which are sequentially stacked on the transparent substrate. And color filter substrate. 2. The first transparent conductive layer is provided only at a predetermined position in a formation region of the color filter layer,
The color according to claim 1, wherein the silane-based surface treatment agent layer is formed on the transparent substrate on which the first transparent conductive layer is not formed and on the first transparent conductive layer. Filter substrate. 3. The first transparent conductive layer is provided only in a predetermined portion of a formation region of the color filter layer,
The color filter substrate according to claim 1, wherein the silane-based surface treatment agent layer is formed only on the first transparent conductive layer. 4. The color filter substrate according to claim 1, further comprising a protective film between the color filter layer and the second transparent conductive layer. 5. A color liquid crystal display device comprising a color filter substrate and a counter electrode substrate facing each other, and a liquid crystal layer sealed between the both substrates, wherein the color filter substrate is defined by any one of claims 1 to 4. A color liquid crystal display device, which is the color filter substrate according to any one of the claims.