JP2002031708A - Color filter and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter with columnar projections for setting the thickness of a liquid crystal layer and a transparent protective layer and to provide a method for producing the color filter. SOLUTION: The color filter has a transparent protective layer 6 comprising a cured body based on an alkali-insoluble silicon-containing resin and transparent columnar projections 7 comprising a cured body based on a photosensitive resin incompatible with the silicon-containing resin and formed at plural prescribed parts on a substrate in,such a way that the projections 7 project from the protective layer. The color filter is produced through a first step in which a colored layer 5 having plural colors in a prescribed pattern is formed on a substrate 2 and a resin composition containing the alkali-insoluble silicon- containing resin and the photosensitive resin incompatible with the silicon- containing resin is applied to form a resin layer comprising a lower layer based on the silicon-containing resin and an upper layer based on the photosensitive resin, a second step in which the resin layer is exposed through a photomask with openings for forming the columnar projections and a third step in which the upper layer of the resin layer is alkali-developed and the resin layer is heated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color filter and a method of manufacturing the same, and more particularly, to a color filter capable of manufacturing a color liquid crystal display device having excellent display quality and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, color liquid crystal display devices have attracted attention as flat displays. As an example of the color liquid crystal display device, a black matrix, a colored layer composed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)), a transparent conductive layer (common electrode), and an alignment layer A color filter comprising: a thin film transistor (TFT element);
There is a type in which a pixel electrode and a TFT array substrate provided with an alignment layer face each other with a predetermined gap therebetween, and a liquid crystal material is injected into the gap to form a liquid crystal layer. In such a color liquid crystal display device, the gap portion is the thickness of the liquid crystal layer itself, and enables good display performance such as high-speed response, high contrast ratio, and wide viewing angle required for the color liquid crystal display device. It is necessary to keep the thickness of the liquid crystal layer, that is, the gap distance between the color filter and the TFT array substrate strictly constant.

Conventionally, as a method of determining the thickness of a liquid crystal layer in a color liquid crystal display device, a color filter and a TFT are used.
There is a method of injecting a liquid crystal in which a number of particles or rods called spacers made of glass, alumina, plastic, or the like are mixed into a gap between the array substrate and the substrate. The size of the gap between the two substrates, that is, the thickness of the liquid crystal layer is determined by the size of the spacer.

However, the above-described color filter and T
The method of forming the gap with the FT array substrate has the following problems in the operation of the color liquid crystal display device.
That is, if the density of the spacers scattered on the substrate surface is appropriate and the spacers are not uniformly dispersed on the substrate surface, a gap portion having a uniform size over the entire surface of the color liquid crystal display device is not formed. . Generally, the scattered amount (density) of the spacer is about 100 / mm ^{2. When a} liquid crystal having a high viscosity is used, the spacer may not be uniformly dispersed after being injected into the gap between the color filter and the TFT array substrate. is there. When such a phenomenon occurs, there is a problem that the display quality of a portion where the spacers are accumulated is deteriorated, and a variation in thickness variation of the gap is increased.

[0005]

In order to solve such a problem, a color filter having a columnar convex portion for determining a gap (the thickness of a liquid crystal layer) has been proposed (JP-A-4-318816). No.). However, in this color filter, after forming a colored layer and applying and forming a protective layer so as to cover the colored layer, a columnar convex portion is formed at a predetermined position on the black matrix by a photolithography process again using a photosensitive resin. Since it is formed, the process is complicated.

[0006] For example, IPS which has recently attracted attention
(In-Plane Switching) In the liquid crystal mode, more precise control of the substrate gap is required than in the TN liquid crystal mode.
In order to meet such demands, in order to make the height accuracy of the columnar protrusions to be ± 0.2 μm or less, a high coating accuracy of the photosensitive resin is required, and throughput, yield, and the like are problematic. .

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is intended to manufacture a color liquid crystal display device having a columnar convex portion for setting the thickness of a liquid crystal layer and a transparent protective layer and having excellent display quality. It is an object of the present invention to provide a color filter that enables the above and a manufacturing method for easily manufacturing such a color filter.

[0008]

In order to achieve the above object, a color filter according to the present invention comprises a substrate, a colored layer of a plurality of colors formed in a predetermined pattern on the substrate, and at least A transparent protective layer formed so as to cover the coloring layer, comprising a transparent columnar convex portion formed at a plurality of predetermined portions on the substrate and projecting from the transparent protective layer, wherein the transparent protective layer is alkali-insoluble. The cured product was mainly composed of a silicon-containing resin, and the column-shaped convex portions were composed of a cured material mainly composed of a photosensitive resin incompatible with the silicon-containing resin.

Further, the color filter of the present invention is configured such that the silicon-containing resin is an acrylic resin. Further, the color filter of the present invention is configured such that the photosensitive resin is a positive photosensitive resin having a styrene skeleton that generates a phenolic hydroxyl group by an acid, or the photosensitive resin has an epoxy group and a carboxyl group. The negative photosensitive resin having a styrene skeleton was used.

[0010] In the method of manufacturing a color filter according to the present invention, after forming a colored layer of a plurality of colors in a predetermined pattern on the substrate, an alkali-insoluble silicon-containing resin is formed on the substrate so as to cover at least the colored layer. And a resin composition containing a photosensitive resin that is incompatible with the silicon-containing resin and a lower layer mainly composed of the silicon-containing resin and an upper layer mainly composed of the photosensitive resin. A first step of forming a layer, a second step of exposing the resin layer through a photomask having an opening for forming a columnar protrusion, and alkali developing the upper layer of the resin layer, By performing a heat treatment on the resin layer, a transparent protective layer made of a cured product containing the silicon-containing resin as a main component is formed so as to cover at least the colored layer, and the transparent protective layer is formed. Third step of forming a plurality of the transparent columnar convex part photosensitive resin comprising a cured product whose main component at a predetermined position, and the like have configure.

In the method of manufacturing a color filter according to the present invention, in the first step, the weight ratio of the silicon-containing resin to the photosensitive resin in the resin composition is 1: 1.
１ ： 1: 5.

According to the present invention, in alkali development after exposing the resin layer, the lower layer mainly composed of a silicon-containing resin remains without dissolving in an alkali developer to form a transparent protective layer, and remains after development. The upper layer of the resin layer is a columnar projection, which has the necessary height as a spacer for setting the thickness of the liquid crystal layer, and can be set with high precision.The transparent protective layer is a color filter. The surface is flattened, the components contained in the colored layer are prevented from being eluted into the liquid crystal layer, and the color filter is obtained with antifouling properties.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will be described below with reference to the drawings. 1. Color Filter of the Present Invention FIG. 1 is a partial plan view showing an example of an embodiment of the color filter of the present invention, and FIG. 2 is a longitudinal sectional view taken along line AA. 1 and 2, a color filter 1 of the present invention includes a substrate 2, a black matrix 3 and a coloring layer 5 formed on the substrate 2, and a transparent protective film covering the black matrix 3 and the coloring layer 5. A layer 6 is formed, and transparent columnar projections 7 are provided at a plurality of predetermined locations (five locations in FIG. 1) of the black matrix 3.
Are formed integrally with the transparent protective layer 6 described above.

Substrate 2 constituting color filter 1 described above
For example, a transparent rigid material having no flexibility such as quartz glass, Pyrex (registered trademark) glass, a synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film or an optical resin plate is used. be able to. Of these, Corning 7059 glass is a material having a low coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the glass. It is suitable for a color filter for a color liquid crystal display device according to the method.

The black matrix 3 constituting the color filter 1 is provided between the display pixel portions composed of the colored layers 5 and outside the region where the colored layers 5 are formed. Such a black matrix 3 is formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 ° by a sputtering method, a vacuum evaporation method, or the like, and patterning the thin film, and containing light-shielding particles such as carbon fine particles. Forming a resin layer of polyimide resin, acrylic resin, epoxy resin, etc., and forming a photosensitive resin layer containing light-shielding particles such as carbon fine particles, metal oxides, etc. The photosensitive resin layer may be formed by patterning the photosensitive resin layer.

The coloring layer 5 has a red pattern 5R, a green pattern 5G, and a blue pattern 5B arranged in a desired pattern shape, and is formed by a pigment dispersion method using a photosensitive resin containing a desired coloring material. And a known method such as a printing method, an electrodeposition method, and a transfer method. In addition, for example, by making the colored pattern 5 thinnest in the red pattern 5R and thickening in the order of the green pattern 5G and the blue pattern 5B, an optimal liquid crystal layer thickness may be set for each color of the colored layer 5. .

The transparent protective layer 6 is provided for flattening the surface of the color filter 1 and for preventing components contained in the colored layer 5 from being eluted into the liquid crystal layer. The thickness of the transparent protective layer 6 depends on the light transmittance of the material used,
It can be set in consideration of the surface condition of the color filter 1 and the like, and for example, can be set in the range of 0.1 to 3.0 μm. Such a transparent protective layer 6 is formed so as to cover at least the colored layer 5 which is in contact with the liquid crystal layer when the color filter 1 is bonded to the TFT array substrate.

The transparent protective layer 6 is made of a cured product containing an alkali-insoluble silicon-containing resin as a main component. Here, in the present invention, the main component means a component occupying 20% by weight or more. As the silicon-containing resin to be used, for example, an acrylic resin containing polysiloxane or silicon in a main chain or a side chain can be mentioned, and one of these can be used alone, or a combination of two or more can be used. Can be used with As described above, since the transparent protective layer 6 is a cured product containing a silicon-containing resin as a main component, in addition to the above-described effects of flattening the surface and preventing the elution of the coloring layer components, it is possible to reduce the contamination of the color filter. The effect will also play.

The columnar projections 7 function as spacers when the color filter 1 is bonded to a TFT array substrate. The columnar protrusions 7 have a certain height so as to protrude from the transparent protective layer 6 in a range of about 2 to 10 μm, and the protrusion amount is required for a liquid crystal layer of a color liquid crystal display device. It can be appropriately set based on the thickness and the like. The formation density of the columnar protrusions 7 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape and material of the columnar protrusions 7, and, for example, the red color forming the colored layer 5 can be set. A necessary and sufficient spacer function is expressed in one set of the pattern 5R, the green pattern 5G, and the blue pattern 5B. In the illustrated example, the shape of the columnar convex portion 7 is a columnar shape, but is not limited thereto, and may be a prismatic shape, a truncated pyramid shape, or the like.

The columnar projections 7 are made of a cured product containing a photosensitive resin as a main component, and the photosensitive resin is incompatible with the silicon-containing resin constituting the transparent protective layer 6. Resin. Here, in the present invention, the main component means a component occupying 20% by weight or more. In addition, incompatible is a blend system in which two phases separated and mixed are not realized in a molecular composition at the stage of a resin composition used in a method for manufacturing a color filter described later. Means that a resin layer composed of a lower layer mainly composed of a silicon-containing resin and an upper layer mainly composed of a photosensitive resin is formed.

The photosensitive resin used may be either a positive photosensitive resin or a negative photosensitive resin. Examples of the positive photosensitive resin include a positive photosensitive resin having a styrene skeleton that generates a phenolic hydroxyl group by an acid. Such a positive photosensitive resin has a phenolic hydroxyl group substituted with a protecting group which is removed by the action of an acid generated from a photoacid generator upon exposure. Examples of the protecting group include an alkoxycarbonyl group (for example, a t-butoxycarbonyl group, an isopropyloxycarbonyl group, a 1-phenylethoxycarbonyl group, a 1,1-diphenylethoxycarbonyl group,
2-cyclohexeneoxycarbonyl group, 2-chloroethoxycarbonyl group, etc., alkoxymethyl group (for example, methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 1-phenoxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group , 4,5-dihydro-2-methylfuran-5-yl group, etc.) and a secondary or tertiary alkyl group having a hydrogen atom at the β-position (eg, t-butyl group, cyclohexyl group, 2-cycloalkyl group). Hexenyl group) is a preferred example.

Examples of the negative photosensitive resin that can be used include, for example, a negative photosensitive resin obtained by adding epoxy to a copolymer of styrene and hydroxystyrene, and a negative photosensitive resin obtained by adding epoxy to a copolymer of styrene and carboxystyrene. A photosensitive resin can be used. The negative photosensitive resin is crosslinked by the presence of a monomer and a polymerization initiator.
The polymerization reaction occurs upon exposure, and the unexposed portions become alkali-soluble.

The above-mentioned columnar projections 7 may be made of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolak epoxy resin, polycarboxylic acid, Glycidyl ester, polyol glycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, copolymerized epoxy compound of glycidyl (meth) acrylate and radically polymerizable monomer Etc. can be contained.

When an alignment layer is provided on the color filter 1 of the present invention having the transparent protective layer 6 and the columnar projections 7 and the alignment processing (rubbing) is performed, and then the TFTs are bonded to a TFT array substrate, the columnar projections 7 A gap is formed between the color filter 1 and the TFT array substrate. And the columnar projection 7 is
Since there is no height accuracy defect due to the leveling phenomenon and no misalignment of each color as seen in the columnar protrusions formed by laminating the three colored layers of R, G and B, Accuracy and position accuracy are extremely high,
Therefore, the gap accuracy between the two substrates is extremely high. Further, even if a part of the columnar convex portion exists in the pixel portion, the display quality is hardly adversely affected because of the transparency. On the other hand, the transparent protective layer 6 flattens the surface of the color filter 1 in which fine irregularities exist,
In addition to reducing the surface roughness that adversely affects the alignment of the liquid crystal, it also prevents a small amount of ionic impurities and the like contained in the coloring layer from being eluted into the liquid crystal layer and adversely affecting display quality. Further, since the transparent protective layer 6 is mainly composed of a cured product of a silicon-containing resin, it also has an effect of preventing the color filter from being contaminated at the time of cutting or transporting. The color filter of the present invention does not include the black matrix 3 as shown in FIG.
What formed the above-mentioned columnar convex part 7 on the top may be used.

Next, an embodiment of a color filter manufacturing method according to the present invention will be described.
FIG. 4 shows an example of the color filter 1 shown in FIGS.
This will be described with reference to FIG.

(First Step) In the first step of the color filter manufacturing method, after forming a colored layer of a plurality of colors in a predetermined pattern on the substrate, an alkali is applied on the substrate so as to cover at least the colored layer. By applying a resin composition containing an insoluble silicon-containing resin and a photosensitive resin that is incompatible with the silicon-containing resin, the lower layer mainly containing the silicon-containing resin and the photosensitive resin are mainly used. A resin layer including an upper layer is formed. That is, first, the substrate 2
A black matrix 3 is formed thereon (FIG. 4A),
Next, a red pattern 5R is formed in a red pattern formation region, a green pattern 5G is formed in a green pattern formation region, and a blue pattern 5B is formed in a blue pattern formation region on the substrate 2 to form a colored layer 5 (FIG. 4B). . Next, a resin layer 8 is formed so as to cover the black matrix 3 and the colored layer 5 (FIG. 4C).

The formation of the black matrix 3 is as follows.
For example, it can be performed as follows. First, a light-shielding layer formed of a metal thin film such as chromium formed by a sputtering method, a vacuum evaporation method, or the like, a resin layer containing light-shielding particles such as carbon fine particles, or the like is formed on the substrate 2, and a known light-shielding layer is formed on the light-shielding layer. A photosensitive resist layer is formed using a positive or negative photosensitive resist. Next, the black matrix 3 is formed by exposing and developing the photosensitive resist layer through a black matrix photomask, etching the exposed light shielding layer, and removing the remaining photosensitive resist layer.

The formation of the colored layer 5 is performed, for example, by
It can be performed as follows. First, a red photosensitive resin layer containing a red coloring material is formed on the substrate 2 so as to cover the black matrix 3, and the red photosensitive resin layer is exposed to light through a predetermined photomask and developed. Thereby, a red pattern 5R is formed in the red pattern forming region on the substrate 2. Hereinafter, similarly, a green pattern 5G is formed in a green pattern formation region on the substrate 2, and further, a blue pattern 5B is formed in a blue pattern formation region on the substrate 2.

The resin layer 8 is formed by optimizing the viscosity of a resin composition containing an alkali-insoluble silicon-containing resin and a photosensitive resin and then applying a known method such as a spin coater or a roll coater. By Black Matrix 3
And it can be applied so as to cover the coloring layer 5 and dried. The applied resin composition undergoes phase separation between the silicon-containing resin and the photosensitive resin, which are incompatible with each other, and a lower layer 8a mainly composed of the silicon-containing resin and an upper layer 8b mainly composed of the photosensitive resin are formed. Is formed. As the alkali-insoluble silicon-containing resin, one kind or a combination of two or more kinds can be used. Such a silicon-containing resin preferably has a molecular weight in the range of 10,000 to 100,000.

As the photosensitive resin, any of the positive photosensitive resin or the negative photosensitive resin described above which has incompatibility with the silicon-containing resin to be used, and A layer in which the upper layer 8b becomes a layer mainly composed of a photosensitive resin by phase separation after coating can be used. Such a photosensitive resin has a molecular weight of 5,000 to 60.
It is preferably in the range of 0000.

When a positive photosensitive resin is used, the resin composition can contain a photoacid generator. The photoacid generator is a compound that is decomposed by light irradiation to generate an acid, and that the generated acid acts on a protective group of the positive photosensitive resin to generate a phenolic hydroxyl group. Is required. Examples of such a photoacid generator include a triazine compound, a diphenyliodonium salt compound, a bis (4-tert-butylphenyl) iodonium salt compound, a triphenylsulfonium salt compound, and a sulfonate compound. More specifically, TEM-Triazine, T, manufactured by Sanwa Chemical Co., Ltd.
Triazine compounds such as FE-triazine, RED-triazine, WS-triazine, dimethoxytriazine, triazine A, S-triazine, TTC-triazine (trade name); DPI-105 manufactured by Midori Kagaku KK;
Diphenyliodonium salt compounds such as MPI-103, BBI-101 and DPI-201 (trade names); TPS-103 and MDS-105 manufactured by Midori Kagaku Co., Ltd.
Triphenylsulfonium salt compounds such as DTS-102, NAT-103, NDS-103 (trade names); TAZ-100, TAZ-1 manufactured by Midori Kagaku Co., Ltd.
04, TAZ-106, TAZ-107, TAZ-11
0, TAZ-111, TAZ-113, TAZ-11
4, TAZ-118, TAZ-123 (trade name)
Triazine compounds; BBI- manufactured by Midori Kagaku Co., Ltd.
Screws (4) such as 101, BB1-201 (above, trade names)
-Tert-butylphenyl) iodonium salt compound;
SI-100, SI-106, P manufactured by Midori Kagaku Co., Ltd.
I-105, NDI-105, NAI-105 (above,
Sulfonate compounds such as (trade name).

When a negative photosensitive resin is used, the resin composition contains a polymerization initiator, a monomer and the like. As the polymerization initiator to be used, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine)
Benzophenone, α-amino acetophenone, 4,4
-Dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorenone, 2,2-diethoxyacetophonone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone , P-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethylether, benzoinbutylether, anthraquinone, 2-tert -Butylanthraquinone, 2-amylanthraquinone, β-chloranthraquinone, anthrone, benzanthrone, dibensuberone, methyleneanthrone , 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene)
-4-methylcyclohexanone, 2-phenyl-1,2
-Butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, -Phenyl-3-ethoxy-propanetrione-
2- (o-benzoyl) oxime, Michler's ketone, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
Morpholinopropan-1-one, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, tetrabromine Photoreducible dyes such as carbonized carbon, tribromophenylsulfone, benzoin peroxide, eosin, methylene blue and ascorbic acid, triethanolamine, 2-
Examples include a combination of reducing agents such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone.

The monomers contained in the resin composition include allyl acrylate, benzyl acrylate,
Butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobonyl acrylate, isodexyl acrylate, Isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate,
Phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3
-Propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate,
Tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyl trimethylolpropane triacrylate , Butylene glycol diacrylate, 1,2,4-butanetriol triacrylate, 2,2,4-trimethyl-1,
3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and the above acrylate changed to methacrylate, γ-methacryloxypropyl trimethoxy Silane, 1-vinyl-
2-pyrrolidone and the like, and these monomers can be used as one kind or as a mixture of two or more kinds.

The weight ratio between the silicon-containing resin and the photosensitive resin in the above resin composition is in the range of 1: 1 to 1: 5, preferably in the range of 1: 1 to 1: 3. If the ratio of the silicon-containing resin in the resin composition is out of the above range, the phase separation between the incompatible silicone-containing resin and the photosensitive resin becomes insufficient, and the coating film has one of the resin phases. The resin layer 8 has a sea-island structure that is a sea or an island, and a substantially flat interface exists between the lower layer 8a mainly composed of a silicon-containing resin and the upper layer 8b mainly composed of a photosensitive resin.

The thickness of the lower layer 8a and the upper layer 8b constituting the resin layer 8 can be arbitrarily controlled by appropriately adjusting the mixing ratio of the silicon-containing resin and the photosensitive resin and the coating thickness. , The thickness of the lower layer 8a is 0.1 to 6
The thickness of the upper layer 8b can be set in the range of 1 to 10 μm.

(Second Step) In the second step of the color filter manufacturing method, the resin layer 8 is exposed through a photomask M for forming a columnar convex portion (FIG. 5A). In this example, the photosensitive resin contained in the upper layer 8b of the resin layer 8 is a negative photosensitive resin. Therefore, an opening m corresponding to the formation pattern of the columnar protrusions 7 is formed in the photomask M used. By this exposure, the curing reaction of the upper layer 8b proceeds in the columnar convex portion forming portion (the exposed portion via the photomask M) of the resin layer 8. The upper layer 8 of the resin layer 8
When the photosensitive resin contained in b is a positive photosensitive resin, the photomask M to be used is provided with a light-shielding portion corresponding to the pattern in which the columnar convex portions 7 are formed.

(Third Step) In the third step of the color filter manufacturing method, the resin layer 8 is developed with an alkali developing solution. In the second step, as described above, a curing reaction has occurred in the upper layer 8b of the resin layer 8 at the position where the columnar protrusions 7 are formed. Absent. However, in the unexposed portion of the resin layer 8, the upper layer 8b dissolves in the alkaline developer. On the other hand, since the lower layer 8a of the resin layer 8 is insoluble in the alkali developing solution, it remains without being dissolved. Thereafter, by performing a post-baking process, a transparent protective layer 6 made of a cured product mainly containing a silicon-containing resin and a transparent columnar convex portion 7 made of a cured product mainly containing a photosensitive resin are formed. The color filter 1 of the present invention is obtained (FIG. 5B).

When the photosensitive resin contained in the upper layer 8b of the resin layer 8 is a positive photosensitive resin, the unexposed portions, ie, the portions where the columnar projections 7 are formed, are almost completely soluble in an alkali developing solution. Does not show sex. Also in this case, the lower layer 8a of the resin layer 8 is insoluble in the alkali developing solution, and thus remains without being dissolved.

The formed transparent protective layer 6 flattens the surface of the color filter 1 in which fine irregularities are present, reduces the surface roughness which adversely affects the alignment of the liquid crystal, and contains a trace amount in the colored layer. This prevents ionic impurities from being eluted into the liquid crystal layer and deteriorating display quality. Further, an effect of preventing the color filter from being contaminated at the time of cutting, transporting, or the like is also exerted.

Further, since the transparent columnar projection 7 is not a laminate of three colored layers of R, G and B, the height accuracy does not decrease due to the leveling phenomenon. Such a transparent protective layer 6 and the columnar convex portions 7 can be simultaneously formed in one photolithography step as described above, and the mixing ratio of the silicon-containing resin and the photosensitive resin and the coating thickness are appropriately adjusted. As a result, the thickness of the transparent protective layer 6 and the columnar convex portions 7
Can be arbitrarily controlled. In the above-described embodiment, the coloring layer 5 is formed by a pigment dispersion method.
The present invention is not limited to this. For example, a dyeing method, a printing method, a transfer method, or the like can be used, and a transparent conductive film may be formed on the substrate 2 in advance, and the electrodeposition method may be used. it can.

[0041]

Next, the present invention will be described in more detail with reference to examples. [Example 1] 300 m as a substrate for a color filter
A glass substrate (Corning 7059 glass) having a size of mx 400 mm and a thickness of 1.1 mm was prepared. After washing the substrate according to a standard method, a light-shielding layer (thickness 0.1 μm) made of metallic chromium
m) was formed. Next, a photosensitive resist is applied to the light-shielding layer by ordinary photolithography,
A black matrix was formed by performing mask exposure, development, etching, and resist layer peeling.

Next, a photosensitive coloring material for a red pattern (Color Mosaic CR-700 manufactured by Fuji Film Ohrin Co., Ltd.) is applied over the entire surface of the substrate on which the black matrix is formed.
1) was applied by spin coating to form a red photosensitive resin layer, and prebaked (85 ° C., 5 minutes). Thereafter, the red photosensitive resin layer is aligned and exposed using a predetermined colored pattern photomask, and is developed with a developing solution (a diluting solution of a color mosaic developing solution CD manufactured by Fuji Film Olin Co., Ltd.). Post bake (200
At 30 ° C. for 30 minutes) to obtain a red pattern (1.5 μm thick) at a predetermined position with respect to the black matrix pattern.
m) was formed.

Similarly, a photosensitive coloring material for a green pattern (Color Mosaic CG-Fuji Film Orin Co., Ltd.)
7001), a green pattern (thickness: 1.5 μm) was formed at a predetermined position with respect to the black matrix pattern. Further, a photosensitive coloring material for a blue pattern (Color Mosaic CB-Fuji Film Olin Co., Ltd.)
7001), a blue pattern (thickness: 1.5 μm) was formed at a predetermined position with respect to the black matrix pattern.

Next, resin compositions 1 to 4 containing a positive photosensitive resin having the following composition were prepared. In each resin composition, the content ratio of the silicon-containing resin and the positive photosensitive resin is set as shown in Table 1 below.

Composition of Resin Composition 1 Silicon-containing resin: 30 parts by weight (methyl methacrylate / acrylate / Si oligomer copolymer (70/20/10)) Positive photosensitive resin: 60 parts by weight (t- A styrene skeleton-containing photosensitive resin having a phenolic hydroxyl group substituted with a butoxycarbonyl group) Photoacid generator: 5 parts by weight (NAI-105 manufactured by Midori Kagaku Co., Ltd.)

Composition of resin composition 2 -Silicon-containing resin: 50 parts by weight (methyl methacrylate / acrylate / Si oligomer copolymer (70/20/10))-Positive photosensitive resin: 50 parts by weight (t- (A styrene skeleton-containing photosensitive resin having a phenolic hydroxyl group substituted with a butoxycarbonyl group) Photoacid generator: 8 parts by weight (NAI-105 manufactured by Midori Kagaku Co., Ltd.)

Composition of resin composition 3 Silicon-containing resin: 60 parts by weight (methyl methacrylate / acrylate / Si oligomer copolymer (70/20/10)) Positive photosensitive resin: 30 parts by weight (t- (A photosensitive resin having a styrene skeleton having a phenolic hydroxyl group substituted with a butoxycarbonyl group) Photoacid generator: 10 parts by weight (NAI-105 manufactured by Midori Chemical Co., Ltd.)

Composition of resin composition 4 Silicon-containing resin: 30 parts by weight (methyl methacrylate / acrylate / Si oligomer copolymer (70/20/10)) Positive photosensitive resin: 180 parts by weight (t- A styrene skeleton-containing photosensitive resin having a phenolic hydroxyl group substituted with a butoxycarbonyl group) Photoacid generator: 5 parts by weight (NAI-105 manufactured by Midori Kagaku Co., Ltd.)

Next, using the above resin compositions 1 to 4,
On the substrate on which the colored layer was formed, the resin was applied by spin coating to form a resin layer having a thickness of 6 μm.
I got As a result of observing the cross sections of the resin layers of Samples 1 to 4, Sample 1 and Sample 2 had a two-layer structure with upper and lower layers due to phase separation. However, in Samples 3 and 4, 1
The layer or one of the resin phases became a sea-island structure in which a part thereof was present, and a two-layer structure was not formed.

Further, using the resin composition 1, a sample 5 having a resin layer thickness of 2 μm and a sample 5 having a resin layer thickness of 10 μm were prepared.
Sample 6 of μm was obtained in the same manner as above. This sample 5
The cross section of the resin layer of Sample 6 had a two-layer structure with upper and lower layers due to phase separation as in Samples 1 and 2. (The above is the first step)

Next, the resin layer of each sample was applied to a 150 mJ / cm ² through a photomask provided with a light shielding portion having a predetermined shape at the position where the columnar convex portion was formed, using a proximity exposure machine using an ultra-high pressure mercury lamp as an exposure light source. Exposure was performed at an exposure amount of (The above is the second step)

Next, each of the substrates of Samples 1 to 6 was immersed in a 0.05% aqueous solution of potassium hydroxide for 15 seconds for development, washed, and post-baked (200 ° C., 200 ° C.) in a clean oven.
30 minutes). (The above is the third step)

By such a series of processing, Sample 1,
From 2, 5, and 6, color filters having structures as shown in FIGS. 1 and 2 could be obtained. The thickness of the transparent protective layer of each color filter and the protruding height of the transparent columnar projection were as shown in Table 1 below.

[0054]

[Table 1]

As is clear from Table 1, the height of the columnar projections and the thickness of the transparent protective layer were adjusted by appropriately adjusting the mixing ratio of the silicon-containing resin and the positive photosensitive resin in the resin composition and the coating thickness. It has been confirmed that it is possible to control at the same time. The color filter obtained from Sample 3 did not have columnar projections, and the color filter obtained from Sample 4 had a portion where a transparent protective layer was not formed, and both were not practically usable. Was.

Example 2 First, resin compositions A to C containing a negative photosensitive resin having the following composition were prepared. In each resin composition, the content ratio of the silicon-containing resin and the negative photosensitive resin is set as shown in Table 2 below.

Composition of resin composition A : Silicon-containing resin: 60 parts by weight (methyl methacrylate / acrylate / Si oligomer copolymer (70/20/10)) Negative photosensitive resin: 120 parts by weight (styrene / (Hydroxystyrene copolymer (60/40)) Monomer: Diethylene glycol diacrylate 50 parts by weight Polymerization initiator 17 parts by weight (Irg907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Epoxy resin: Novolac epoxy resin 25 weights Department

Composition of resin composition B : Silicon-containing resin: 80 parts by weight (methyl methacrylate / acrylate / Si oligomer copolymer (70/20/10)) Negative photosensitive resin: 80 parts by weight (styrene / (Hydroxystyrene copolymer (60/40)) Monomer: Diethylene glycol diacrylate 30 parts by weight Polymerization initiator 10 parts by weight (Irg907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Epoxy resin: Novolac epoxy resin 15% by weight Department

Composition of resin composition C : Silicon-containing resin: 120 parts by weight (methyl methacrylate / acrylate / Si oligomer copolymer (70/20/10)) Negative photosensitive resin: 60 parts by weight (styrene / (Hydroxystyrene copolymer (60/40)) Monomer: Diethylene glycol diacrylate: 25 parts by weight Polymerization initiator: 10 parts by weight (Irg907 manufactured by Ciba Specialty Chemicals Co., Ltd.) Epoxy resin: Novolac epoxy resin: 15 parts by weight Department

Next, using the above resin compositions A to C,
Samples A to C were obtained by forming a photosensitive resin layer having a thickness of 6 μm on the substrate on which the black matrix and the colored layer were formed in the same manner as in Example 1. As a result of observing the cross sections of the resin layers of Samples A to C, Sample A and Sample B had phase separation and had a two-layered structure. However, in sample C, 1
The layer or one of the resin phases became a sea-island structure in which a part thereof was present, and a two-layer structure was not formed.

A sample D having a resin layer thickness of 3 μm and a resin layer having a thickness of 9 μm were prepared using the resin composition A.
Sample E having m was obtained in the same manner as above. The cross section of the resin layer of each of Samples D and E had a two-layer structure in which phase separation occurred similarly to Samples A and B. (that's all,
1st process)

Next, the resin layer of each sample was placed at 250 mJ / cm ² through a photomask provided with an opening having a predetermined shape at the position where the columnar convex portion was formed, using a proximity exposure machine using an ultra-high pressure mercury lamp as an exposure light source. Exposure was performed at an exposure amount of (The above is the second step)

Next, the substrates of Samples A to E were immersed in a 0.05% aqueous potassium hydroxide solution for 40 seconds for development, washed, and post-baked (200 ° C., 200 ° C.) in a clean oven.
30 minutes). (The above is the third step)

By such a series of processing, the sample A,
From B, D, and E, a color filter having a structure as shown in FIGS. 1 and 2 could be obtained. The thickness of the transparent protective layer of each of the color filters and the protruding height of the transparent columnar protrusion were as shown in Table 2 below.

[0065]

[Table 2]

As is apparent from Table 2, the height of the columnar protrusions and the thickness of the transparent protective layer were adjusted by appropriately adjusting the mixing ratio of the silicon-containing resin and the negative photosensitive resin in the resin composition and the coating thickness. It has been confirmed that it is possible to control at the same time. The color filter obtained from Sample C had a portion where no columnar convex portion was formed, and was not practically usable.

[0067]

As described above in detail, according to the present invention, the plurality of transparent columnar projections have a height required as a spacer for setting the thickness of the liquid crystal layer, and the height is set with excellent precision. Even if there is a part of the columnar convex portion in the pixel portion, the display quality is hardly adversely affected because it is transparent, and the transparent protective layer flattens the color filter surface. In addition, since the components contained in the colored layer are prevented from being eluted into the liquid crystal layer, a highly reliable color liquid crystal display device having excellent display quality can be obtained, and a cured product of the silicon-containing resin constituting the transparent protective layer can be obtained. Thereby, the stain resistance of the color filter can be obtained. Further, in the present invention, such a columnar convex portion and the transparent protective layer are used a resin composition containing an alkali-insoluble silicon-containing resin and a photosensitive resin incompatible with the silicon-containing resin. Since it can be formed in a single photolithography process, the process becomes simple, and furthermore, by appropriately adjusting the mixing ratio of the silicon-containing resin and the photosensitive resin and the coating thickness, the height of the columnar protrusions and the transparent protective layer The thickness of the liquid crystal layer can be controlled at the same time, and a color liquid crystal display device that requires high precision in controlling the thickness of the liquid crystal layer, for example, IPS (In
-Plane Switching) It can correspond to the color liquid crystal display device of the liquid crystal mode. In addition, since the silicon-containing resin is insoluble in the alkali developer, a transparent protective layer having a desired thickness can be formed stably, and the development time can be easily controlled.

[Brief description of the drawings]

FIG. 1 is a partial plan view showing an example of an embodiment of a color filter of the present invention.

FIG. 2 is a diagram illustrating a color filter according to the present invention shown in FIG.
It is a longitudinal cross-sectional view in the A line.

FIG. 3 is a longitudinal sectional view showing another embodiment of the color filter of the present invention.

FIG. 4 is a process chart illustrating an example of a method for manufacturing a color filter of the present invention.

FIG. 5 is a process chart illustrating an example of a method for manufacturing a color filter of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Color filter 2 ... Substrate 3 ... Black matrix 5 ... Coloring layer 6 ... Transparent protective layer 7 ... Columnar convex part 8 ... Resin layer 8a ... Lower layer 8b ... Upper layer M ... Photomask

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/038 501 G03F 7/038 501 4J002 7/039 601 7/039 601 7/075 521 7/075 521 7/11 501 7/11 501 7/40 501 7/40 501 F term (reference) 2H025 AA02 AA18 AB13 AC01 AD01 AD03 BC37 BC81 BC83 BC85 BE00 BE10 BG00 CB17 CB41 CB51 DA02 DA03 DA31 FA17 FA29 2H048 BA02 BA11 BA28 BA28 BA29 BA55 BA62 BB02 BB08 BB14 BB15 BB22 BB28 BB37 BB43 2H089 LA09 MA04X NA14 PA05 QA14 TA12 TA13 2H091 FA04Y FA35Y FA50Y FB04 FC10 LA12 2H096 AA30 BA05 BA11 BA20 GA08 4J002 BC04X BC12X BG05W BG05W

Claims (6)

[Claims] 1. A substrate, a colored layer of a plurality of colors formed in a predetermined pattern on the substrate, a transparent protective layer formed so as to cover at least the colored layer, and a plurality of predetermined layers on the substrate. A transparent columnar projection formed at a site and protruding from the transparent protection layer, wherein the transparent protection layer is a cured product mainly containing an alkali-insoluble silicon-containing resin, and the columnar projection is formed of the silicon-containing resin. A color filter, which is a cured product mainly composed of a photosensitive resin incompatible with a resin. 2. The color filter according to claim 1, wherein the silicon-containing resin is an acrylic resin. 3. The color filter according to claim 1, wherein the photosensitive resin is a positive photosensitive resin having a styrene skeleton generating a phenolic hydroxyl group by an acid. 4. The color filter according to claim 1, wherein the photosensitive resin is a negative photosensitive resin having a styrene skeleton having an epoxy group and a carboxyl group. 5. After forming a colored layer of a plurality of colors in a predetermined pattern on a substrate, an alkali-insoluble silicon-containing resin and a silicon-containing resin are formed on the substrate so as to cover at least the colored layer. A first step of applying a resin composition containing a photosensitive resin that is incompatible with each other to form a resin layer including a lower layer mainly composed of the silicon-containing resin and an upper layer mainly composed of the photosensitive resin; A second step of exposing the resin layer through a photomask having an opening for forming a columnar convex portion, alkali developing the upper layer of the resin layer, and thereafter subjecting the resin layer to a heat treatment By forming a transparent protective layer made of a cured product containing the silicon-containing resin as a main component so as to cover at least the colored layer, the photosensitive resin is formed at a plurality of predetermined sites on the transparent protective layer. The third step, the color filter manufacturing method characterized by having a forming the transparent columnar convex part comprising a cured product composed mainly. 6. The method according to claim 5, wherein in the first step, the weight ratio of the silicon-containing resin to the photosensitive resin in the resin composition is in a range of 1: 1 to 1: 5. 3. The method for producing a color filter according to item 1.