JPH10170712A - Color filter substrate and its production, and liquid crystal element using the element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively produce a color filter having excellent heat resistance, solvent resistance and definition, and free from color mixing. SOLUTION: A light shieldable resin compsn. layer 2 and a photosensitive resin compsn. layer 3 contg. silicon atoms at the main chain or side chains are formed on a light transparent substrate 1 and the light shieldable resin compsn. layer 2 is patterned by using a silicone resin layer 4 formed by patterning and exposing using a photomask as a mask, by which black matrices 5 are formed. Inks 7a to 7c of R, G, B are, thereupon, imparted to the apertures of the black matrices 5 by an ink jet system, thereby, the color filters consisting of colored parts 8a to 8c are formed.

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 filter substrate used in a color liquid crystal display used for a color television, a personal computer, a pachinko game console, etc., and more particularly, to a method for manufacturing the same using an ink jet system. Further, the present invention relates to a color filter substrate obtained by the manufacturing method and a liquid crystal element using the substrate.

[0002]

2. Description of the Related Art In recent years, the development of personal computers,
In particular, with the development of portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, tends to increase. However, for further widespread use, it is necessary to reduce the cost of the liquid crystal display. In particular, there is an increasing demand for reducing the cost of a color filter having a high cost. Conventionally, various manufacturing methods have been tried to satisfy the above-mentioned requirements while satisfying the required characteristics of the color filter, but a method that satisfies all the required characteristics has not yet been established. The respective methods will be described below.

[0003] The first method is a dyeing method. In the dyeing method, a water-soluble polymer material, which is a material for dyeing, is applied on a glass substrate, and is patterned into a desired shape by a photolithography process. Get a pattern. This is repeated three times to form R (red), G (green), and B (blue) colored layers, thereby forming a color filter.

[0004] Another example of this dyeing method is disclosed in JP-A-5-28.
No. 8913 describes a method of providing a photosensitive layer on a substrate, exposing the photosensitive layer in a pattern, and dyeing an unexposed portion. This process is repeated three times to obtain R, G, B
It is described that a color filter consisting of three colors is manufactured.

[0005] The second method is a pigment dispersion method, which is recently replacing the dyeing method. In this method, a photosensitive resin layer in which a pigment is dispersed is formed on a substrate, and a monochromatic pattern is obtained by patterning the photosensitive resin layer. Further, by repeating this step three times, R, G, and B colored layers are formed to form a color filter.

A third method is an electrodeposition method. In this method, a transparent electrode is patterned on a substrate, and immersed in an electrodeposition coating solution containing a pigment, a resin, an electrolytic solution, and the like to electrodeposit a first color. This process is repeated three times to form R, G, and B colored layers, and finally fired to form a color filter.

As a fourth method, a pigment is dispersed in a thermosetting resin, and printing is repeated three times so that R, G,
After separately applying B, a colored layer is formed by thermally curing the resin to form a color filter. Also,
In any method, a protective film is generally formed on the colored layer.

What is common to these methods is that R,
It is necessary to repeat the same process three times in order to color the three colors G and B, which increases the cost. In addition, there is a problem that the yield decreases as the number of steps increases. Further, in the electrodeposition method, since the pattern shape that can be formed is limited, it is difficult to apply the current technology for TFT. Further, the printing method is not suitable for forming a fine pitch pattern due to poor resolution.

[0009]

SUMMARY OF THE INVENTION In order to make up for these drawbacks, Japanese Patent Application Laid-Open Nos. 59-75205 and 63-23
Japanese Patent Application Laid-Open No. 5901 or Japanese Patent Application Laid-Open No. 1-217302 describes a method of manufacturing a color filter by using an ink jet method, but a satisfactory one has not yet been obtained.

[0010] In particular, when a color filter is manufactured by the ink jet method, there is a problem of color mixing between adjacent color filters of different colors. Therefore, as a method for preventing color mixture between color filters, Japanese Patent Laid-Open No.
There is a proposal described in Japanese Patent Publication No. 3005. The method is
This is a method in which a pattern of silicone rubber having large water repellency and oil repellency is formed on a black matrix to prevent color mixing in an ink jet method or a printing method. However, a method of forming a silicone rubber pattern is to remove the silicone rubber layer or the silicone rubber layer and the photosensitive resin layer by photolithography after forming the silicone rubber layer on the photosensitive resin layer.
This requires two coating steps, which is disadvantageous in the manufacturing process.

Japanese Patent Application Laid-Open No. 7-35916 proposes a method for obtaining a black matrix having a water-repellent and oil-repellent surface by a simpler method. In this publication, a light-transmissive photosensitive resin layer containing silicone fine particles is formed on a member for forming a black matrix, and the photosensitive resin layer is patterned by a photolithography process. A method for processing a black matrix forming member using a resin layer as a mask is described.

[0012] However, according to this proposal, since silicone is contained in the photosensitive resin in the form of fine particles, (1) the fine silicone particles become development residues, which are transferred to the black matrix forming member to cause black matrix defects. (2) When the added amount of the silicone fine particles is increased, the resolution deteriorates, so that it is not suitable for forming a fine pattern. (3) Since the added amount of the silicone fine particles is limited, high ink repellency can be obtained. There are problems such as difficulty.

An object of the present invention is to provide a highly reliable color filter which satisfies required characteristics such as heat resistance, solvent resistance, and resolution, and which prevents color mixing even by an ink jet system, at low cost. It is in.

[0014]

A first aspect of the present invention is a method of manufacturing a color filter substrate having a black matrix and a color filter located at an opening of the black matrix on a light transmitting substrate. Forming a light-shielding resin composition layer on a transparent substrate, and, on the light-shielding resin composition layer, a photosensitive resin composition mainly composed of a soluble silicone resin containing a silicon atom in a main chain or a side chain. A step of forming a layer, a step of patterning the photosensitive resin composition layer by photolithography and partially removing the same, and a step of forming the light-shielding resin composition layer using the patterned photosensitive resin composition layer as a mask. By patterning and removing a part, a step of forming a black matrix, and applying an ink to the opening of the black matrix by an ink jet method Forming a color filter,
It is characterized by having.

The second aspect of the present invention is a color filter substrate manufactured by the above manufacturing method, and the third is a liquid crystal element characterized by using the color filter substrate.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. FIG. 1 is a process chart showing one embodiment of the manufacturing method of the present invention. Hereinafter, (a) to (e) of FIG. 1 are cross-sectional views corresponding to the following steps -a to e.

Step-a A light-shielding resin composition layer 2 and a photosensitive resin composition layer 3 are formed on a light-transmitting substrate 1.

In the present invention, a glass substrate is generally used as the light-transmitting substrate. However, the glass substrate satisfies the characteristics required for final use such as a liquid crystal display device, for example, transparency, mechanical strength, etc., and withstands post-processing. The material is not limited to a glass substrate.

The light-shielding resin composition layer 2 is finally used as a black matrix, as described later, and needs to have sufficient light-shielding properties. Furthermore, since it is necessary to perform patterning in a post-process,
It is necessary to have good solubility in an alkali aqueous solution or an organic solvent, or good etching characteristics by oxygen plasma.

Specifically, a resin composition in which a light-shielding substance such as a black pigment or a black dye is dispersed or mixed in a polyvinylphenol-type resin, a phenol novolak-type resin, or the like is preferably used, but is not limited thereto. Not something.
In the present invention, the light-shielding resin composition layer 2 can be formed by a coating method such as spin coating, roll coating, bar coating, spray coating, or dip coating. Further, the coating film thickness can be arbitrarily set as long as a sufficient light shielding property can be obtained when a black matrix is used. In particular, patterning using a photolithography process, unlike a black matrix photoresist material used as a black matrix as it is, since the light-shielding resin composition according to the present invention does not require photosensitivity, It is possible to increase the amount of the light-shielding substance added, and there is an advantage that a light-shielding property necessary for functioning as a black matrix with a small film thickness can be obtained.

Next, as the photosensitive resin composition layer 3 used in the present invention, an ink-repellent portion for preventing color mixture between adjacent colored portions when applying ink by an ink-jet method described later. A photosensitive resin composition having a high water- and oil-repellent property and a soluble silicone resin containing a silicon atom in a main chain or a side chain as a main component is used.

In the present invention, as the soluble silicone resin, either a negative type in which the light-irradiated portion is insolubilized or a positive type in which the light-irradiated portion is solubilized can be used. Specifically, as the negative type, a system in which bisazide is added to siloxane or silsesquioxane having an unsaturated group, or a system in which a crosslinking agent and an acid generator are added to an alkali-soluble silicone resin are used. As the positive type, a system in which a naphthoquinonediazide ester is added to an alkali-soluble siloxane or silsesquioxane, or a system in which a dissolution inhibitor and an acid generator are added to a similar alkali-soluble silicone resin, an alkali-soluble novolak A system obtained by adding a naphthoquinonediazide ester to a silicone-modified type resin, or a system obtained by adding a dissolution inhibitor and an acid generator to a similar novolak-type resin, a silicone-modified main chain-degradable acrylic resin, polysilane Etc. can be used.

In order to completely prevent color mixing of ink, it is preferable to use a soluble silicone resin having higher ink repellency. More specifically, the content of silicon atoms is preferably 10% by weight or more, and in particular, a polymer compound having a siloxane structure or a polysilane structure having a high silicon atom content in a main chain or a side chain is suitably used.

In the present invention, the photosensitive resin composition layer 3 can be formed by a coating method such as spin coating, roll coating, bar coating, spray coating, and dip coating. Further, the coating thickness is within a range in which a sufficient resistance to an alkaline aqueous solution, an organic solvent, oxygen plasma or the like used for removing a part of the light-shielding resin composition layer can be obtained, and a sufficient solution for patterning can be obtained. It can be set arbitrarily as long as the image quality is obtained. In order to obtain sufficient resistance to alkaline aqueous solution, organic solvent, oxygen plasma, etc., it is effective to increase the film thickness,
To obtain high resolution, it is effective to reduce the film thickness.

Step-b The photosensitive resin composition layer 3 is subjected to pattern exposure and development processing using a photomask to be patterned to form a silicone resin layer 4 having a desired pattern.

Step-c Using the silicone resin layer 4 as a mask, the light-shielding resin composition is patterned to form a black matrix 5. Specifically, dissolution removal with an alkaline aqueous solution or an organic solvent, dry etching with oxygen plasma, or the like can be used. In particular, when an alkali-developable silicon compound is used as the photosensitive resin composition, and a compound that is soluble in an aqueous alkali solution is used as the light-shielding resin composition, the light-shielding property is simultaneously with the development of the photosensitive resin composition layer 3. The resin composition layer 2 can be dissolved and removed, and the process can be greatly simplified.

In consideration of the rectangularity of the light-shielding resin composition, generation of residues, and the like, dry etching using oxygen plasma is effective.

Step-d The inks 7a to 7c of R, G, and B colors are applied to the openings of the black matrix 5 using the ink jet head 6, and the inks are dried if necessary. The color filter 8 includes the colored portions 8a to 9c of B.

In the present invention, as the ink used for forming the color filter, both dye-based and pigment-based inks can be used. In consideration of the process resistance, reliability, and the like in the post-process, a component that is cured by heat treatment or light irradiation and fixes the dye or pigment used as a colorant of the ink, that is, a crosslinkable monomer or polymer, etc. It is preferable that the curable ink contains the following components.

Further, as the ink jet system, a bubble jet type using an electrothermal converter or a piezo jet type using a piezoelectric element can be used as an energy generating element, and the coloring area and the coloring pattern can be set arbitrarily. can do.

In the present invention, the black matrix 5
Since the silicone resin layer 4 having ink repellency is provided on the ink, the ink on the resin layer 4 is repelled and smoothly stored in each opening, so that the ink between the adjacent colored portions Ink mixing is prevented.

Step-e A protective film 9 is formed on the color filter 8 if necessary. As the protective film, a photo-curable type, a thermo-curable type, or a photo-thermal type resin material, an inorganic film formed by vapor deposition, sputtering or the like can be used, and the transparency as a color filter is not impaired. Any material can be used as long as it can withstand a process, for example, a process such as ITO or alignment film formation.

FIG. 2 is a sectional view of one embodiment of a liquid crystal element using the color filter substrate of the present invention. In the figure, 11
Is a light-transmitting substrate similar to the substrate 1, 12a and 12b are electrodes, 13a and 13b are alignment films, 14 is liquid crystal, and 15a and
15b is a polarizing plate. This embodiment uses a TFT (not shown)
This is an active matrix type liquid crystal element using.

A method for manufacturing the liquid crystal device shown in FIG. 2 will be described. On the protective film 8 of the color filter substrate described above,
The (common) electrode 12b and the alignment film 13b are formed. on the other hand,
On the opposing substrate 11, TFTs (not shown) and (pixel) electrodes 12a are formed in a matrix, and an alignment film 13a is formed thereon. These substrates are arranged facing each other such that the colored portions 8a to 8c of the color filter 8 are arranged at positions facing the pixel electrodes 12a, adhered via a sealing material, and filled in the gaps with the liquid crystal compound 14. Thus, the liquid crystal element shown in FIG. 2 is configured. The surfaces of the alignment films 13a and 13b are usually subjected to an alignment treatment such as a rubbing treatment, so that liquid crystal molecules can be arranged in a certain direction.

Further, polarizing plates 15a and 15b are adhered to the outside of the substrates 1 and 11, respectively.

As a backlight, a combination of a fluorescent lamp and a scattering plate (not shown) is generally used, and the liquid crystal element functions as an optical shutter for changing the transmittance of light 20 of the backlight. Is displayed.

The liquid crystal compound used in the present invention is not particularly limited, and may be a TN type liquid crystal or a ferroelectric liquid crystal (F
LC) and the like are preferably used. In addition, the present invention is not limited to the active matrix type liquid crystal element described in the above embodiment, but may be, for example, a simple matrix type liquid crystal element.

Further, the color filter substrate of the present invention can be suitably used for devices other than liquid crystal devices.

[0039]

【Example】

Example 1 A light-shielding resin composition layer obtained by dispersing a black pigment in a cresol novolak resin was formed on a glass substrate to a thickness of 1 μm. Further, a soluble silicone resin comprising an alkali-soluble polysilsesquioxane and a naphthoquinonediazide ester is coated with a 0.3 μm-thick film.
Then, pre-baking was performed at 90 ° C. for 20 minutes to form a soluble silicone resin layer.

Next, 300 m is passed through a photomask.
A black matrix substrate having a silicone resin layer formed on the surface by pattern exposure with an exposure amount of J / cm ² and immersion in an aqueous alkali solution to remove a part of the soluble silicone resin layer and the light-shielding resin composition layer. I got

Next, using an ink jet recording apparatus,
Each of thermosetting R, G, and B inks composed of water, an organic solvent, a melamine resin, and a pigment is applied to the openings of the black matrix to form R, G, and B matrix patterns. For 5 minutes and subsequently at 230 ° C. for 30 minutes to cure the ink, thereby forming a color filter comprising R, G, and B colored portions.

Further, a two-component thermosetting resin SS-7625 (manufactured by JSR) was spin-coated so as to have a thickness of 1 μm as a protective film, and was cured by heat treatment at 230 ° C. for 1 hour.

When the thus prepared color filter substrate for a liquid crystal device was observed with an optical microscope, no color mixture was observed.

Example 2 A light-shielding resin composition layer obtained by mixing an alkali-soluble acrylic resin and a black dye was formed on a glass substrate to a thickness of 1 μm. Further, a polysilane having a phenyl group and a methyl group in a side chain was spin-coated so as to have a thickness of 0.3 μm, and prebaked at 90 ° C. for 20 minutes to form a polysilane layer.

Then, 200 m is passed through a photomask.
A black matrix substrate having a silicone resin layer formed on the surface is obtained by pattern exposure with an exposure amount of J / cm ² and immersion in an aqueous alkali solution to remove a part of the polysilane layer and the light-shielding resin composition layer. Was.

Next, using an ink jet recording apparatus,
Each of thermosetting R, G, and B inks composed of water, an organic solvent, an acrylic resin, and a pigment is applied to the openings of the black matrix to form R, G, and B matrix patterns. For 5 minutes and subsequently at 230 ° C. for 30 minutes to cure the ink, thereby forming a color filter comprising R, G, and B colored portions.

Further, a two-component thermosetting resin SS-6500 (manufactured by JSR) was spin-coated so as to have a film thickness of 1 μm as a protective film, and cured by heat treatment at 230 ° C. for 1 hour.

When the thus prepared color filter substrate for a liquid crystal element was observed with an optical microscope, no color mixture was observed.

Example 3 A light-shielding resin composition layer formed by mixing an alkali-soluble acrylic resin and a black dye was formed on a glass substrate to a thickness of 1 μm. Further, a polysilane having a phenyl group and a methyl group in a side chain was spin-coated so as to have a thickness of 0.3 μm, and prebaked at 90 ° C. for 20 minutes to form a polysilane layer.

Then, 200 m is passed through a photomask.
After pattern exposure of the polysilane layer by pattern exposure at an exposure amount of J / cm ² and patterning of the polysilane layer, dry etching is performed by oxygen plasma to remove a part of the light-shielding resin composition layer, thereby forming a silicone on the surface. A black matrix substrate on which a resin layer was formed was obtained.

Next, using an ink jet recording apparatus,
Thermosetting R, consisting of water, melamine resin and dye,
After applying the G and B inks to the openings of the black matrix to form R, G and B matrix patterns,
The ink was cured by performing a heat treatment at 90 ° C. for 5 minutes and subsequently at 230 ° C. for 30 minutes to form a color filter composed of R, G, and B colored portions.

Further, as a protective film, a two-component thermosetting resin SS-7625 (manufactured by JSR) was spin-coated so as to have a thickness of 1 μm, and cured by heat treatment at 230 ° C. for 1 hour.

When the color filter substrate for a liquid crystal element thus produced was observed with an optical microscope, no color mixture was observed.

Comparative Example A photoresist material for a black matrix (manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated on a glass substrate so as to have a thickness of 1.2 μm.
A pre-bake for minutes was performed. Next, pattern exposure is performed through a photomask at an exposure amount of 200 mJ / cm ² ,
A black matrix substrate was manufactured by performing a development process.

Next, using an ink jet recording apparatus, thermosetting R, G, and B inks composed of water, a melamine resin, and a dye are applied to the openings of the black matrix, and the R, G, and B inks are applied. After forming the matrix pattern, a heat treatment was performed at 90 ° C. for 5 minutes and then at 230 ° C. for 30 minutes to cure the ink, thereby forming a color filter including R, G, and B colored portions.

Further, a two-component thermosetting resin SS-7625 (manufactured by JSR) was spin-coated so as to have a film thickness of 1 μm as a protective film, and cured by heat treatment at 230 ° C. for 1 hour.

When the thus prepared color filter substrate for a liquid crystal element was observed with an optical microscope, mixed colors were observed.

[0058]

As described above, according to the present invention,
A color filter that satisfies required characteristics such as heat resistance, solvent resistance, and resolution and that does not cause color mixture can be manufactured at low cost, and a highly reliable liquid crystal element can be provided at low cost.

[Brief description of the drawings]

FIG. 1 is a process chart showing one embodiment of a manufacturing method of the present invention.

FIG. 2 is a sectional view of one embodiment of the liquid crystal element of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 light-transmitting substrate 2 light-shielding resin composition layer 3 photosensitive resin composition layer 4 silicone resin layer 5 black matrix 6 inkjet head 7 a to 7 c ink 8 a to 8 b coloring portion 8 color filter 9 protective film 11 light-transmitting substrate 12 a , 12b Electrode 13a, 13b Alignment film 14 Liquid crystal compound 15a, 15b Polarizer 20 Light

Claims (9)

[Claims] 1. A method of manufacturing a color filter substrate having a black matrix on a light-transmitting substrate and a color filter positioned at an opening of the black matrix, comprising: forming a light-shielding resin composition layer on the light-transmitting substrate. Forming,
A step of forming a photosensitive resin composition layer containing a soluble silicone resin containing a silicon atom in a main chain or a side chain as a main component on the light-shielding resin composition layer; A step of patterning by lithography to remove a part, and a step of patterning the light-shielding resin composition layer using the patterned photosensitive resin composition layer as a mask and partially removing the same to form a black matrix, Forming a color filter by applying ink to the openings of the black matrix by an ink jet method. 2. The production of a color filter substrate according to claim 1, wherein the patterning of the light-shielding resin composition layer is carried out by treating the photosensitive resin composition layer with an aqueous alkaline solution or an organic solvent using the patterned photosensitive resin composition layer as a mask. Method. 3. The method for producing a color filter substrate according to claim 1, wherein the patterning of the photosensitive resin composition layer and the patterning of the light-shielding resin composition layer are simultaneously performed. 4. The patterning of the light-shielding resin composition layer is performed by treating the photosensitive resin composition layer with oxygen plasma using the patterned photosensitive resin composition layer as a mask.
A manufacturing method of the color filter substrate according to the above. 5. The method according to claim 1, wherein the ink contains a crosslinking component. 6. The method according to claim 5, wherein the ink has a red color, a green color, and a blue color. 7. A color filter substrate manufactured by the manufacturing method according to claim 1. 8. The color filter substrate according to claim 7, further comprising a protective film on the color filter. 9. A liquid crystal device comprising a pair of electrode substrates sandwiching a liquid crystal, and using the color filter substrate according to claim 7 as one of the electrode substrates.