JP2003121633A - Color filter, liquid crystal display device and manufacturing method for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter having color brilliance equal to that of a printed matter and capable of exhibiting excellent display without defects such as disconnection of ITO and to provide a liquid crystal display device. SOLUTION: The color filter is characterized in that the area of a triangle formed by connecting each chromaticity coordinates of red, green and blue in the XYZ color specification system measured by using a light source C is not smaller than 80% to the NTSC standard and pixels with one or more colors are formed by laminating a layer containing a photosensitive resin on a colored layer containing a non-photosensitive resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter and a liquid crystal display device using the same, and more particularly to a color filter having a wide color reproduction range and a liquid crystal display device.

[0002]

2. Description of the Related Art At present, liquid crystal display devices, which are lightweight, thin, and have low power consumption, are used for notebook PCs, portable information terminals,
It is used in various applications such as digital cameras. LCD display characteristics (brightness, color reproducibility, viewing angle characteristics, etc.)
As a result, the use of liquid crystal display devices is being expanded to desktop monitor applications in addition to conventional notebook PC applications. Furthermore, recently, a large-sized LCD TV has been developed that further improves the color reproducibility of a desktop monitor, and the color reproduction range of the CRT (NTSC (Nati
About 70% of the onal Television System Committee) is being reproduced.

The color characteristics of a CRT are red, green, blue, and X for each color.
The chromaticity coordinates (x, y) in the YZ color system chromaticity diagram are red (0.640, 0.330) and green (0.290, respectively).
0.600), E which is blue (0.150, 0.060)
BU (European Broadcasting
Although it is almost equal to the Union standard, a display having a color reproduction range conforming to the EBU standard is particularly poor in the color reproduction range in the green region, and it is difficult to display vivid colors like printed matter. Color reproducibility is wider than EBU standard,
Good standards include the NTSC standard, which includes red, green, blue,
Chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram of each color
Are red (0.670, 0.330) and green (0.2
10, 0.710) and blue (0.140, 0.080).

In order to manufacture a liquid crystal display device having a wide color reproduction range, the pixels of the color filter should be darkened.
The darkening method is the pigment of the color filter paste /
There is a method of increasing the pigment concentration of the resin component. However, when the color filter paste is a negative photosensitive acrylic material, there is a problem that if the pigment concentration is increased, photocuring does not proceed in the photolithography processing step of color filter production, and thus it cannot be processed. When the color filter paste is a non-photosensitive material, photolithography is performed using a photosensitive material such as a positive resist, but in the positive resist stripping process, the pattern is cracked or missing due to the stripping solvent. Or a problem occurs. As a method of darkening the color without increasing the pigment concentration, there is a method of increasing the film thickness of the pixel.
However, by increasing the thickness of conventional color filters for desktop monitors or LCD TVs, NT
If the color reproduction range is widened as in the SC standard, it is difficult to form a uniform pattern in a single-layer pixel having a large film thickness, and the pixel taper becomes large, resulting in a decrease in resolution.

[0005]

SUMMARY OF THE INVENTION The present invention was devised in view of the above-mentioned drawbacks of the prior art. It has a practical film thickness without increasing the pigment concentration of the color filter paste, and has good processing accuracy. NT without increasing the manufacturing process
It is to provide a liquid crystal display device that realizes high color reproducibility equivalent to SC.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the problems of the prior art, the inventors of the present invention can realize a high color reproduction range equivalent to NTSC by the following color filters, It was also found that it can be manufactured at low cost. That is, (1) the area of the triangle connecting the chromaticity coordinates of red, green, and blue in the XYZ color system chromaticity diagram measured using the C light source is 80% or more of the NTSC standard ratio, and one or more colors 2. The color filter according to claim 1, wherein the colored layer containing a photosensitive resin is laminated on the colored layer containing a non-photosensitive resin. (2) The color filter according to (1), wherein the non-photosensitive resin is a polyimide resin and the photosensitive resin is an acrylic resin. (3) The film thickness of the photosensitive resin is non-photosensitive. The color filter according to claim 1, wherein the color filter has a film thickness of not more than that of the resin. (4) The color filter according to any one of claims 1 to 3, wherein the film thickness of each pixel is 0.8 µm or more and 5 µm or less. (5) The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using the C light source are 0.635 ≦ x ≦ 0.6.
The color filter according to any one of claims 1 to 4, wherein the color filter has a red pixel satisfying each expression of 80 and 0.300 ≤ y ≤ 0.350. (6) The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using the C light source are 0.190 ≦ x ≦ 0.3.
20. The color filter according to any one of claims 1 to 4, wherein the color filter has a green pixel satisfying each equation of 0.580≤y≤0.685. (7) The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using the C light source are 0.130 ≦ x ≦ 0.1.
60, The color filter according to any one of claims 1 to 4, which has a blue pixel satisfying each formula of 0.040 ≤ y ≤ 0.100. (8) A color filter in which an area of a triangle connecting red, green, and blue chromaticity coordinates in an XYZ color system chromaticity diagram measured using a C light source has an NTSC standard ratio of 80% or more, After applying the color paste containing the uncured non-photosensitive resin and then applying the color paste containing the uncured photosensitive resin, the non-photosensitive resin and the photosensitive resin are simultaneously patterned by one photolithography process. A method of manufacturing a color filter for a liquid crystal display device, comprising: (9) A liquid crystal display device using the color filter according to any one of claims 1 to 8.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The color filter of the present invention has at least three color pixels of red, green and blue, and the red, green in the XYZ color system chromaticity diagram measured using a C light source, Area of a triangle formed by connecting each chromaticity coordinate of blue (color reproduction range)
Is preferably 80% or more of the NTSC standard ratio. This is because when the color filter is in this range, a display quality as good as that of printed matter can be obtained when the color filter is used in a liquid crystal display device. And it is more preferably 85% or more, further preferably 90% or more, and most preferably 95% or more.

The chromaticity range (x, y) of each color pixel, which is preferable for obtaining a good display comparable to that of a printed matter, is 0.63.
Red pixels satisfying the respective expressions of 5 ≦ x ≦ 0.680 and 0.300 ≦ y ≦ 0.350, 0.190 ≦ x ≦ 0.320,
A green pixel satisfying each expression of 0.580 ≦ y ≦ 0.685,
0.130 ≦ x ≦ 0.160, 0.040 ≦ y ≦ 0.1
Is a blue pixel satisfying each formula of 00, and more preferably,
0.645 ≦ x ≦ 0.680, 0.300 ≦ y ≦ 0.3
Red pixel satisfying each equation of 40, 0.200 ≦ x ≦ 0.3
10, green pixels satisfying the respective expressions of 0.600 ≦ y ≦ 0.685, 0.130 ≦ x ≦ 0.160, 0.040 ≦ y ≦
A blue pixel satisfying each equation of 0.090, and more preferably 0.655 ≦ x ≦ 0.680, 0.300 ≦ y ≦
Red pixel satisfying each equation of 0.330, 0.200 ≦ x ≦
Green pixels satisfying the respective equations of 0.300, 0.625 ≦ y ≦ 0.685, 0.130 ≦ x ≦ 0.160, 0.040
A blue pixel satisfying each expression of ≦ y ≦ 0.080, and most preferably 0.665 ≦ x ≦ 0.680, 0.300.
0.200, a red pixel satisfying each expression of ≦ y ≦ 0.330
Green pixels satisfying the respective expressions of ≦ x ≦ 0.300, 0.650 ≦ y ≦ 0.685, 0.130 ≦ x ≦ 0.160, 0.
It is a blue pixel that satisfies each expression of 040 ≦ y ≦ 0.070.

In each color pixel, in a region where the color is lighter than the above chromaticity range, display with high color reproducibility cannot be obtained, which is not preferable. Further, in a region where the color is darker than the above chromaticity range, the pixel transmittance becomes low, and the brightness of the liquid crystal display device is lowered, which is not preferable.

One or more kinds of various pigments can be used in order to obtain a pixel having the above-mentioned color characteristics, and other pigments may be added as long as the color characteristics are not impaired. Examples of typical pigments include Pigment Red (PR-), 2, 3, 22, 3
8, 149, 166, 168, 177, 209, 22
4,242,254, Pigment Orange (PO-)
5, 13, 17, 31, 36, 38, 40, 42, 4
3, 51, 55, 59, 61, 64, 65, 71, Pigment Yellow (PY-) 12, 13, 14, 17, 2
0, 24, 83, 86, 93, 94, 109, 110,
117, 125, 137, 138, 139, 147, 1
48, 150, 153, 154, 166, 173, 18
5, Pigment Blue (PB-) 15 (15: 1, 1
5: 2, 15: 3, 15: 4, 15: 6), 21, 2
2, 60, 64, Pigment Violet (PV-) 1
9, 23, 29, 32, 33, 36, 37, 38, 4
0, 50, Pigment Green (PG-) 7, 10, 3
6, 47 and the like. In the present invention, various pigments can be used without being limited to these, but a pigment is appropriately selected from the viewpoint that it has high color tone and coloring power and can be formed into a thin film.

The red pixel is preferably toned by including at least one of PR-254 and PR-177, and more preferably toned by combining both PR-254 and PR-177. . As a red pixel, PR-
When both 254 and PR-177 are used for toning, the weight ratio of PR-177 in all pigments is 3 to 50%,
The weight ratio of PR254 is preferably 50 to 97%, and the weight ratio of PR177 is 15 to 50%.
More preferably, the weight ratio of 4 is 50 to 85%. The composition of the colorant in the non-photosensitive resin of the red pixel and the composition of the colorant in the photosensitive resin do not have to be the same. For example, in a non-photosensitive resin, PR-254 is added to the red pixel in the total pigment ratio of 50 to 50.
97% can be added, and PR-177 can be added to the photosensitive resin in an amount of 3 to 50% in terms of the total red pixel pigment.

The green pixel is PG-7 as the main pigment and PY-12, PY-13, PY-17, PY-8 as the sub-pigments.
3, PY-109, PY-110, PY-138, PY
-139, PY-150, and PY-185 are preferably included in the toning, and as the sub-pigment of the green pixel, PY-17, PY-138, and P are particularly preferable.
It is more preferable that the color tone is adjusted to include at least one of Y-139 and PY-150. When toning is performed using PG7 as a green pixel, the weight ratio of PG7 in all pigments is preferably 40 to 90%, and 50 to 50%.
It is more preferably 85%. When PY-17 is used as a sub-pigment for a green pixel, the weight ratio of PY-17 in all pigments is preferably 20 to 60%, more preferably 30 to 60%. PY-
138, PY-138 in all pigments
Is preferably 20 to 60% by weight, and 30
It is more preferably -60%. When toning is performed using PY-139, the weight ratio of PY-139 in all pigments is preferably 5 to 40%, more preferably 5 to 30%, and preferably 5 to 20%. Is more preferable. When toning is performed using PY-150, the weight ratio of PY-150 in all pigments is preferably 5 to 50%, more preferably 5 to 40%, and 10 to 10%.
More preferably, it is 40%. Further, as described above, these yellow pigments may be used in combination of two or more.

The composition of the colorant in the non-photosensitive resin of the green pixel and the composition of the colorant in the photosensitive resin do not have to be the same. For example, PG7 is added to the non-photosensitive resin at a weight ratio of 40 to 90% of all green pixel pigments, and P is added as a sub-pigment to the photosensitive resin.
Y-17 is 2% by weight of PY-17 in the total amount of green pixel pigment.
0-60% can be put.

The blue pixel is PB-15: 6 as the main pigment,
It is preferable that PV-23 is included as a sub-pigment and toning is performed. When PB-15: 6 and PV-23 are combined for toning as a blue pigment, PB-15: PB-15 in all pigments:
It is preferable that the weight ratio of 6 is 70 to 90%, the weight ratio of PV-23 is 10 to 30%, the weight ratio of PB-15: 6 is 75 to 90%, and the weight ratio of PV-23 is 10%.
Is more preferably 25%, the weight ratio of PB-15: 6 is 75-85%, and the weight ratio of PV-23 is 15%.
More preferably, it is -25%.

The composition of the colorant in the non-photosensitive resin of the blue pixel and the composition of the colorant in the photosensitive resin do not have to be the same. For example, PB-15: 6 may be added to the non-photosensitive resin in an amount of 70 to 90% of the total blue pixel pigment, and PV-23 may be added to the photosensitive resin in an amount of 10 to 30% of the total amount of the blue pixel pigment. it can.

Colorant / resin component ratio (wt%) in the photosensitive resin in order to increase the resolution of each pattern of red, green and blue
Is preferably 50/50 or less, more preferably 40 /
It is 60 or less, more preferably 30/70 or less.

In the liquid crystal display device of the present invention, it is important that the layer containing the photosensitive resin is formed on the colored layer containing the non-photosensitive resin laminated on the color filter.

Here, the non-photosensitive resin means a resin whose dissolution rate in a developing solution does not change depending on the presence or absence of light irradiation when the uncured resin is mainly irradiated with light such as ultraviolet rays. The resin refers to a resin whose dissolution rate in a developing solution changes depending on the presence or absence of light irradiation when the uncured resin is mainly irradiated with light such as ultraviolet rays. In the photosensitive resin, the resin in the light-irradiated part is cured by a photoreaction and the solubility in the developing solution is lowered. Generate,
There is a positive type in which pattern processing can be performed by improving the solubility in a developing solution.

By stacking a layer containing an uncured photosensitive resin on a colored layer containing an uncured non-photosensitive resin and performing photolithography, the photosensitive resin and the non-photosensitive resin can be simultaneously processed. . When patterning a non-photosensitive resin, it is necessary to stack a positive photoresist, photolithographically process it, and remove the photoresist.The non-photosensitive resin is cracked or missing by the photoresist stripping solution. There is a possibility. When the photosensitive resin of the present invention is laminated, since the photosensitive resin layer is a colorless transparent layer or a colored layer, it is possible to produce a color filter without peeling off the photosensitive resin after photolithography processing, and it is non-photosensitive. The resin is not exposed to the resist stripping solution, and the photoresist stripping process can be shortened. N
In order to achieve the TSC standard of 80% or more, it is necessary to increase the pigment concentration of the color filter paste or increase the film thickness. When the photosensitive resin layer is a colored layer containing a pigment, by stacking the photosensitive resin layer and the non-photosensitive resin layer, the chromaticity is obtained by adding the pigment concentration of each layer, so that the thickness of the NTSC is not increased so much. The standard of 80% or more can be achieved.

When the NTSC standard of 80% or more is achieved in a single layer, the film thickness becomes large, so that in-plane uniformity and resolution during processing tend to be deteriorated. However, in the present invention, the photosensitive resin layer has a pigment concentration. Lower the non-photosensitive resin to increase the pigment concentration, 1
The processing accuracy can be improved by reducing the film thickness per layer. The preferable colorant / resin component ratio (wt%) in each color pixel of the colored layer containing a non-photosensitive resin is preferably 30/70 or more, and more preferably 35/65 or more in the red pixel. In the green pixel, it is preferably 40/60 or more, more preferably 45/55 or more. In the blue pixel, it is preferably 20/80 or more, more preferably 25/75 or more. If the amount of the resin component is too small, the film thickness can be reduced, but pattern peeling due to a decrease in adhesion to the substrate or cracks due to a decrease in coating film strength may occur, which makes pattern formation difficult. . On the other hand, if the amount of the pigment is too small, the degree of coloring is lowered, and the film thickness for obtaining a predetermined chromaticity becomes large, which may cause a problem of a step on the color filter surface or a problem of pattern resolution. Even if the layer containing the photosensitive resin contains a coloring material,
It does not have to be included. When the photosensitive resin layer is a colored layer containing a coloring material, the total chromaticity of the layer containing the non-photosensitive resin and the coloring material is reduced, and thus the film thickness becomes smaller, which is preferable. When the colorant component of the photosensitive resin layer is 50 (vol%) or more, it is not preferable because the photoreaction is difficult to proceed in the exposure step of the photolithography process and the pattern resolution is lowered.
As the method for measuring the vol% of the pigment, the specific gravity of the acrylic resin (about 1.3) and the specific gravity of the polyimide resin (about 1.4) can be understood because the pigment used is known from the chromaticity of the color filter and the spectrum. ) And film thickness
ol% can be estimated. In addition, the cross-section SEM (or TE
There is a method of calculating the volume from the image of M).

Blue pixels and red pixels are NTSC standard 80%
Since the colorant ratio for achieving the above chromaticity may be small, there is little problem of pattern resolution deterioration due to strong positive resist stripping solution resistance and thick film. In some cases, it is not necessary to laminate the resin.

In order not to reduce the pattern resolution,
It is important that the film thickness of the photosensitive resin is equal to or less than the film thickness of the non-photosensitive resin. When the photosensitive resin is collectively exposed in the exposure process of photolithography, the light from the photomask wraps around and the pattern resolution decreases. The wider the exposure gap between the photomask and the color filter substrate and the thicker the photosensitive resin film, the lower the pattern resolution. Since the non-photosensitive resin is not affected by the wraparound of light from the photomask in the exposure process, it has a better resolution than the photosensitive resin. In the present invention, a pattern with good resolution can be obtained by making the photosensitive resin thin so as not to cause coating unevenness. In the non-photosensitive paste and the photosensitive paste, the solid content concentration of the resin component and the pigment combined is 2 to 40 from the viewpoints of coating properties and drying properties.
%, Preferably 3 to 30%, more preferably 5 to 25
Used in the range of%.

As the non-photosensitive resin material of the present invention, materials such as polyimide resin, epoxy resin, acrylic resin, urethane resin, polyester resin and polyolefin resin are preferably used. As the photosensitive resin, polyimide resin, epoxy resin, acrylic resin,
Materials such as urethane resin, polyester resin, and polyolefin resin are preferably used. Here, the polyimide resin is not particularly limited,
A polyamic acid which is a polyimide precursor and is imidized by heating or an appropriate catalyst is preferably used. The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine.

In the synthesis of the polyamic acid in the present invention, for example, an aliphatic or alicyclic tetracarboxylic dianhydride can be used. Specific examples thereof include 1,2, 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,5-cyclopentane tetracarboxylic dianhydride, 1,2, 4,5-bicyclohexene tetracarboxylic dianhydride, 1,2,
4,5-cyclohexanetetracarboxylic dianhydride,
1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione and the like can be mentioned. When an aromatic type is used, a polyamic acid that can be converted into a film having good heat resistance can be obtained. As a specific example thereof, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid can be obtained. Dianhydride, pyromellitic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4' -Oxydiphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ", 4,4"- Paraterphenyl tetracarboxylic acid dianhydride and 3,3 ", 4,4" -metaterphenyl tetracarboxylic acid dianhydride are mentioned. Further, when a fluorine-based one is used, a polyamic acid that can be converted into a film having good transparency in the short wavelength region can be obtained, and as a specific example thereof, 4,4 ′-(hexafluoroisopropylidene) can be obtained. ) Diphthalic anhydride and the like. The present invention is not limited to these, and one or more tetracarboxylic dianhydrides may be used.

In the synthesis of the polyamic acid in the present invention, as the diamine, for example, an aliphatic or alicyclic diamine can be used, and specific examples thereof include ethylenediamine and 1,3-diamino. Cyclohexane, 1,4-diaminocyclohexane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane,
4,4'-diamino-3,3'-dimethyldicyclohexyl and the like can be mentioned. When an aromatic type is used, a polyamic acid that can be converted into a film having good heat resistance can be obtained, and specific examples thereof include 4,4′-diaminodiphenyl ether and 3,4′-diamino. Diphenyl ether, 4,4'-diaminodiphenylmethane,
3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diamino Toluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3
′ -Dimethylbenzidine, 3,3′-dimethoxybenzidine, o-tolidine, 4,4 ″ -diaminoterphenyl, 1,5-diaminonaphthalene, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4, 4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
Examples thereof include bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, and bis [4- (3-aminophenoxy) phenyl] sulfone. Further, when a fluorine-based one is used, a polyamic acid that can be converted into a film having excellent transparency in a short wavelength region can be obtained. As a specific example thereof, 2,2-bis [4- (4 -Aminophenoxy)
Phenyl] hexafluoropropane and the like.

When siloxane diamine is used as a part of the diamine, the adhesiveness with the inorganic substrate can be improved. The siloxane diamine is usually used in an amount of 1 to 20 mol% based on all diamines. If the amount of siloxane diamine is too small, the effect of improving the adhesiveness will not be exhibited, and if it is too large, the heat resistance will decrease. Specific examples of the siloxane diamine include bis-3- (aminopropyl) tetramethylsiloxane. The present invention is not limited to this, and one or more diamines may be used. The synthesis of polyamic acid is generally carried out by mixing tetracarboxylic dianhydride and diamine in a polar organic solvent and reacting them. At this time, the degree of polymerization of the obtained polyamic acid can be adjusted by the mixing ratio of the diamine and the tetracarboxylic dianhydride. In addition, there are various methods for obtaining a polyamic acid, such as reacting tetracarboxylic acid dichloride with a diamine in a polar organic solvent and then removing hydrochloric acid and the solvent to obtain a polyamic acid. However, the present invention can be applied to polyamic acid regardless of the synthetic method.
Next, the repeating number of the structural unit of the polyamic acid used in the color paste of the present invention will be described. The higher the molecular weight, the better the mechanical properties of the polyimide film. Therefore, it is desired that the polyimide precursor polyamic acid also has a large molecular weight. On the other hand, when patterning the polyamic acid film by wet etching, if the molecular weight of the polyamic acid is too large, there is a problem that the time required for development becomes too long. Therefore, the preferable range of the number of repeating structural units is 15 to 1000, more preferably 18 to 400, and further preferably 20 to 100. Since the molecular weight of polyamic acid generally varies, the preferable range of the number of repeating structural units here is 50% of all polyamic acid within this range.
It means that it is contained in an amount of mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more.

An acrylic resin will be described as an example of the resin for the photosensitive color paste. The acrylic resin generally has a structure containing at least an acrylic polymer, an acrylic polyfunctional monomer or oligomer, and a photopolymerization initiator in order to have photosensitivity. The acrylic polymer that can be used is not particularly limited, but a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinylacetic acid, and acid anhydrides.
These may be used alone or in combination with another copolymerizable ethylenically unsaturated compound. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate and methacrylic acid. Isopropyl, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert acrylate
-Butyl, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, unsaturated carboxylic acid alkyl esters such as benzyl methacrylate, styrene, p -Aromatic vinyl compounds such as methylstyrene, o-methylstyrene, m-methylstyrene and α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl such as glycidyl acrylate and glycidyl methacrylate Ester, vinyl acetate, carboxylic acid vinyl ester such as vinyl propionate, acrylonitrile,
Methacrylonitrile, vinyl cyanide compounds such as α-chloroacrylonitrile, 1,3-butadiene, aliphatic conjugated dienes such as isoprene, acryloyl group at each terminal, or polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, Examples thereof include macromonomers such as polybutyl acrylate, polybutyl methacrylate, and polysilicone, but are not limited thereto.

Further, an acrylic polymer having an ethylenically unsaturated group added to its side chain is preferably used because the sensitivity during processing is improved. Examples of the ethylenically unsaturated group include vinyl group, allyl group, acryl group and methacryl group. As a method of adding such a side chain to an acrylic (co) polymer, when the acrylic (co) polymer has a carboxyl group, a hydroxyl group, or the like, an ethylenically unsaturated compound having a glycidyl group is added to these. In general, a method of addition reaction with acrylic acid or methacrylic acid chloride is used. In addition, a compound having an ethylenically unsaturated group can be added using isocyanate. Examples of the ethylenically unsaturated compound having a glycidyl group or acrylic acid or methacrylic acid chloride as used herein include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, crotonic acid glycidyl ether, and isocrotonic acid glycidyl. Examples thereof include ether, acrylic acid chloride and methacrylic acid chloride.

Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid. Oligomer such as ester, propylene oxide propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, alkyd modified (meth) acrylate, or tripropylene glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, triacrylformal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate. These can be used alone or in combination. Further, the following monofunctional monomers can also be used in combination, for example, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butyl methacrylate, glycidyl methacrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, etc.,
A mixture of two or more of these or a mixture with another compound is used. By selecting and combining these polyfunctional and monofunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the paste. In particular, a methacrylate compound is preferable to an acrylate compound for increasing hardness, and a compound having 3 or more functional groups is preferable for increasing sensitivity. Further, melamines, guanamines and the like can be preferably used instead of the acrylic monomer. The photopolymerization initiator is not particularly limited, and known ones can be used, for example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2 , 2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone,
Thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1
-[4- (Methylthio) phenyl] -2-morpholino-1
-Propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-
Chlor-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzanthraquinone, 1,4-
Examples thereof include dimethylanthraquinone, 2-phenylanthraquinone, and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. Further, other acetophenone-based compounds, imidazole-based compounds, benzophenone-based compounds, thioxanthone-based compounds, phosphorus-based compounds, triazine-based compounds, and inorganic photopolymerization initiators such as titanates can also be preferably used. Further, it is preferable to add a sensitization aid such as p-dimethylaminobenzoic acid ester because the sensitivity can be further improved. Further, two or more kinds of these photopolymerization initiators can be used in combination.

The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 1 to the total solid content of the paste.
30 wt%, more preferably 5 to 25 wt%, and further preferably 10 to 20 wt%.

As the solvent in the color paste used in the present invention, a solvent that dissolves the polyamic acid or acrylic resin used can be used. As the solvent for dissolving the polyamic acid, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Amide polar solvents such as N, N-dimethylformamide, β-propiolactone, γ-butyrolactone, γ-
Examples thereof include lactones such as valerolactone, δ-valerolactone, γ-caprolactone and ε-caprolactone. In addition, in the case of an acrylic resin, in addition to these, for example, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, ethylene glycol or propylene glycol derivatives such as propylene glycol monoethyl ether, or propylene glycol monoethyl ether. Acetate, ethyl acetoacetate, methyl-3-methoxypropionate, 3
-Methyl-3-methoxybutyl acetate and other aliphatic esters, or ethanol, 3-methyl-3-
It is also possible to use aliphatic alcohols such as methoxybutanol and ketones such as cyclopentanone and cyclohexanone. Therefore, as the solvent for the color paste used in the present invention, it is preferable to use a single solvent in which the resin used is dissolved or a mixed solvent of two or more kinds of solvents in an appropriate combination. In this case, a poor solvent for the resin to be used can be used as the auxiliary solvent. The preferred solvent is not particularly limited, but includes, for example, a mixed solvent of N-methylpyrrolidone and cyclopentanone, and in the case of an acrylic resin, cyclopentanone alone can be preferably used. ..
In the step of forming pixels, a paste containing an uncured non-photosensitive resin is applied on a transparent substrate, heated and dried (semi-cure), and then a paste containing an uncured photosensitive resin is applied on the non-photosensitive resin. , Semi-cure. As a method for applying the uncured resin, a dip method, a roll coater method, a spinner method, a die coating method, a wire bar coating method, or the like is preferably used, and thereafter, semi-cure is performed using an oven or a hot plate. Although the semi-cure conditions vary depending on the resin used, the solvent, and the resin coating amount, it is usually preferable to heat at 60 to 200 ° C. for 1 to 60 minutes.

After semi-curing, mask exposure and photolithography of alkali development develop the pattern of the photosensitive resin, and the non-photosensitive resin is patterned in accordance with the pattern. A pixel of one color can be formed by photolithography. As the alkaline developer, both an organic alkaline developer and an inorganic alkaline developer can be used. As the inorganic alkaline developer, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is preferably used. As the organic alkali developing solution, an aqueous solution of tetramethylammonium hydroxide or an amine-based aqueous solution such as methanolamine is preferably used. The alkali development can be performed by dip development, shower development, paddle development, or the like. After the development, washing with pure water is performed to remove the alkaline developer. In the shower development, it is preferable to adjust the shower pressure so as to obtain the optimum pixel shape. If the shower pressure is weak, the resolution of pixels is reduced. If the shower pressure is strong, the pixel may peel off from the substrate. The shower pressure is preferably 0.05 to 5 MPa. After alkali development, it is dried by heating (main curing). The curing conditions are slightly different depending on the type of resin and the coating amount, but it is generally to heat at 150 to 300 ° C. for 1 to 60 minutes.

In the color filter of the present invention, the total pixel thickness for each color of the layer containing the non-photosensitive resin and the layer containing the photosensitive resin is preferably 0.8 μm or more and 5 μm or less. More preferably, 1.0 μm or more and 4.0 μm
It is the following. If the film thickness exceeds 5 μm, the level difference on the surface of the color filter becomes large, and even if an overcoat is formed on the color filter to flatten it, ITO breakage or liquid crystal alignment failure may occur. Pixels having a film thickness exceeding 5 μm are difficult to form a pattern, and developing a thick film lowers the resolution, which is not preferable. When the film thickness is 0.5 μm or less, there is a high possibility that coating defects such as pinholes will occur when each color pixel paste is applied, and it is difficult to form a uniform coating film. The film thickness of each of the photosensitive resin and the non-photosensitive resin is not particularly specified, but the pixel thickness of the colored layer containing the non-photosensitive resin is preferably 0.8 μm or more and 4 μm or less, more preferably 1.0 μm or more 3 0.5 μm
It is the following. The thickness of the layer containing the photosensitive resin is 0.8 μm
It is preferably 3 μm or less and more preferably 1.0 μm
It is 2 μm or less. The thickness of the layer containing the photosensitive resin is 3
If it is more than μm, the resolution in photolithography processing is lowered, which is not preferable. An example of the color filter manufacturing method of the present invention will be described. When forming a non-photosensitive resin,
A color paste containing at least a polyamic acid, a colorant, and a solvent is applied on a transparent substrate, and then a polyamic acid colored coating film is formed by air drying, heat drying, vacuum drying, or the like. In the case of heat drying, it is preferable to use an oven, a hot plate, or the like, and perform the heating in the range of 50 to 180 ° C. for 1 to 60 minutes. Next, the polyamic acid colored coating film thus obtained is coated with a paste composed of an acrylic polymer, an acrylic polyfunctional monomer, a photosensitive acrylic resin containing a photopolymerization initiator, a coloring agent, and a solvent, and then air-dried. By heat-drying, vacuum-drying, etc., a photosensitive acrylic colored coating film is laminated. In the case of heating and drying, use an oven, hot plate, etc., and
It is preferable to carry out for 60 minutes to 60 minutes. Then, a photomask is placed on the photosensitive acrylic film, and ultraviolet rays are irradiated using an exposure device. After the exposure, the photosensitive acrylic colored coating and the polyamic acid colored coating are simultaneously etched with an alkali developing solution.

The polyamic acid colored coating is then converted into a polyimide colored coating by heat treatment. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 350 ° C., preferably 18 ° C.
It is carried out continuously or stepwise at a temperature of 0 to 250 ° C. for 0.5 to 5 hours.

For the pixels on which the photosensitive acrylic colored film is not laminated, a polyamic acid colored film is formed and then a photoresist is applied to form a photoresist film. Then, a photomask is placed on the photoresist film and irradiated with ultraviolet rays using an exposure device. After the exposure, the photoresist coating and the polyamic acid coating are simultaneously etched with an alkaline developer. After etching, the photoresist film that is no longer needed is removed.

When the above steps are performed for the red, green, and blue color pastes and the color pastes for laminated color materials, and if necessary, the black color paste, a color filter for a liquid crystal display device can be manufactured.

Next, an example of a liquid crystal display device produced by using this color filter will be described. A transparent protective film is formed on the color filter, and I is further formed on the transparent protective film.
A transparent electrode such as a TO film is formed. Next, this color filter substrate and a reflective electrode substrate on which a reflective electrode such as a metal vapor deposition film is formed, and a liquid crystal alignment film that has been subjected to a rubbing treatment for liquid crystal alignment provided on those substrates,
And via a spacer for maintaining the cell gap,
Face and stick together. In addition, on the reflective electrode substrate,
In addition to the reflection electrode, a projection for light diffusion, a thin film transistor (TFT) element or a thin film diode (TFD) element, a scanning line, a signal line, and the like are provided, and a TFT liquid crystal display device,
A TFD liquid crystal display device can be created. Next, after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed. Next, the module is completed by mounting an IC driver or the like.

[0038]

[Example] <Measurement method> Transmittance, color coordinates: Otsuka Electronics Co., Ltd.
Using an MCPD-2000 microspectrophotometer manufactured by Mfg. Co., Ltd., measurement was performed using a glass on which ITO was formed, which was formed under the same film forming conditions as those formed on the color filter, as a reference. The transmission region chromaticity here is obtained from a spectrum obtained when the above-mentioned color filter transmission region is measured by a microspectrophotometer, and the reflection region chromaticity is a colored region in the region. Is obtained by squaring the spectral spectrum of the above and the spectral spectrum of the transparent area at each wavelength, and taking the weighted average of the areas of the colored area and the transparent area. Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited thereto.

Example 1 A. Preparation of Polyamic Acid Solution 95.1 g of 4,4′-diaminodiphenyl ether and 6.2 g of bis (3-aminopropyl) tetramethyldisiloxane were charged together with 525 g of γ-butyrolactone and 220 g of N-methyl-2-pyrrolidone,
After adding 144.1 g of 3 ', 4,4'-biphenyltetracarboxylic dianhydride and reacting at 70 ° C for 3 hours, 3.0 g of phthalic anhydride was added and further reacting at 70 ° C for 2 hours. , 25% by weight polyamic acid solution (P
AA) was obtained.

B. Synthesis of polymer dispersant 4,4'-diaminobenzanilide 161.3 g,
3,3'-diaminodiphenyl sulfone 176.7
g, and 18.6 g of bis (3-aminopropyl) tetramethyldisiloxane with γ-butyrolactone 2667
g, N-methyl-2-pyrrolidone (527 g), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (439.1 g) was added, and the mixture was reacted at 70 ° C. for 3 hours, and then phthalic anhydride was added. 2.2g was added and another 7
The reaction was carried out at 0 ° C. for 2 hours to obtain a polymer dispersant (PD) which was a 20% by weight polyamic acid solution.

C. Preparation of non-photosensitive color paste Pigment Red PR254, 2.88 g (60 wt% of the entire pigment), Pigment Red PR177, 1.92
g (40 wt%) and polymer dispersant (PD) 22.67
g and γ-butyrolactone 81.4 g were charged together with 90 g of glass beads, and a homogenizer was used.
After dispersing at 000 rpm for 5 hours, filter the glass beads,
Removed. In this way, a 6% dispersion liquid solution (GD) of PR254 and PR177 was obtained.

A solution prepared by diluting 12.24 g of polyamic acid solution (PAA) with 32.95 g of γ-butyrolactone and 18.80 g of 3-methoxy-3-methyl-1-butanol was added to 54.44 g of dispersion (GD) and mixed. Then, a red color paste (R-1) was obtained. The pigment / polymer ratio of this paste is 49/51. Similar to the red paste, the weight composition of the pigment is PG7 / PY17 = 65/3.
5, green polymer (G-1) having a pigment polymer ratio (weight ratio) = 63/37, PB15: 6 / PV23 = 80/2
A blue paste (B-1) having a ratio of 0 and a pigment polymer ratio (weight ratio) of 35/65 was prepared.

E. Preparation of photosensitive color paste Pigment Red PR254, 1.5 g (6% of the entire pigment)
0 wt%), Pigment Red PR177, 1.0 g
(40 wt%) and 50 g of 3-methyl-3-methoxybutanol were charged, and a homogenizer was used to measure 700
After dispersing at 0 rpm for 5 hours, the glass beads were filtered and removed. Acrylic copolymer solution (CYCLOMER P, ACA-250, 43 wt% solution manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, pentaerythritol tetramethacrylate 30.0 g as a polyfunctional monomer, and “Irgacure” 369 15 as a photopolymerization initiator. A red (R-2) was obtained by adding 61.03 g of a photosensitive resin solution (solid content concentration 20% by weight) in which 260 g of cyclopentanone was added to 0.0 g. The pigment / polymer ratio (weight ratio) of this paste is 17
/ 83. Similar to the red paste, the green composition (G-2), P, in which the pigment weight composition is PG7 / PY17 = 65/35, and the pigment / polymer ratio (weight ratio) = 3/97.
A blue paste (B-2) having B15: 6 / PV23 = 80/20 and a pigment polymer ratio (weight ratio) = 10/90 was prepared.

E. Preparation and Evaluation of Colored Coating Film 240 of non-photosensitive red paste (R-1) prepared in D was formed on a glass substrate on which a black matrix was patterned.
It was applied by a spinner so that the film thickness after heat treatment at 30 ° C. for 30 minutes would be 2.5 μm, dried in an oven at 120 ° C. for 20 minutes, and the photosensitive red paste (R-2) was dried at 240 ° C. for 30 minutes. It was applied by a spinner so that the film thickness after heat treatment for 1 minute would be 1.0 μm, and dried in an oven at 80 ° C. for 10 minutes.
Using a UV photo-exposure machine and a chrome photomask 1
It was exposed to 00 mJ / cm ² (ultraviolet intensity of 365 nm).
After the exposure, the substrate was immersed in a developer containing a 2.0% aqueous solution of tetramethylammonium hydroxide, the colored coating film of the photosensitive resin and the polyamic acid coating film were simultaneously edged, and then rinsed with water. Further, the colored coating film of the photosensitive resin and the colored coating film of the polyamic acid were simultaneously heat-treated at 240 ° C. for 30 minutes to obtain a red pattern. Next, the non-photosensitive green paste (G-1) was applied by a spinner so that the film thickness after heat treatment at 240 ° C. for 30 minutes would be 2.5 μm, and 120 ° C.
After drying in an oven for 20 minutes, the photosensitive green paste (G-2) was heat-treated at 240 ° C. for 30 minutes to give a film thickness of 1.
It was applied by a spinner so as to have a thickness of 0 μm, and dried in an oven at 80 ° C. for 10 minutes. A green pattern was obtained by etching and heat treatment similar to the red pattern. Next, non-photosensitive blue paste (B-1) was applied by a spinner so that the film thickness after heat treatment at 240 ° C. for 30 minutes would be 2.5 μm, and 1
It is dried in an oven at 20 ° C. for 20 minutes, and a photosensitive blue paste (B-2) is applied thereto by a spinner so that the film thickness after heat treatment at 240 ° C. for 30 minutes is 1.0 μm, and then 80 ° C.
Oven dried for 10 minutes. A blue pattern was obtained by etching and heat treatment similar to the red pattern. Red-green,
The blue pattern had a thickness of 4.5 μm in each case. Further, on the obtained color filter, an overcoat agent "Optomer" (SS6917 + SS091) manufactured by JSR Corporation
7) is formed into a film having a thickness of 1 μm, and an ITO film is further formed thereon to 0.1 μm.
Sputtering was performed so that the film thickness was 4 μm.

The chromaticity (x, y) of the color filter thus obtained when passing through the C light source is red (0.675, 0.316) and green (0.201, 0.6), respectively.
82) and blue (0.145, 0.045), and the color reproduction range was 101.9% of the NTSC standard.

Separately, a TFT element on non-alkali glass,
A substrate on which pixel electrodes and the like were formed was prepared as a counter substrate, and an alignment film was printed and rubbed on the substrate (colored layer substrate) coated with the color paste and the counter substrate to orient. A sealant in which microrods were kneaded was printed on one of these two substrates, a bead spacer having a thickness of 5 μm was dispersed, and then the two substrates were bonded together. Next, TN liquid crystal (refractive index anisotropy Δn to 0.1) compatible with 4 V driving was injected to close the liquid crystal injection port with a sealing agent. A liquid crystal cell filled with liquid crystal was sandwiched between orthogonal polarizing films to prepare a liquid crystal cell for evaluation. A liquid crystal display device was completed by mounting an IC driver or the like on the liquid crystal cell. The image quality of the obtained liquid crystal display device was capable of displaying vivid colors close to those of printed matter.

The obtained display device was disassembled, the color filter with the alignment film was taken out, and the chromaticity of the color filter when passing through the C light source was measured in the same manner as above.
Red (0.675, 0.316), green (0.201, 0.
682), blue (0.145, 0.045), and the color reproduction range is 101.9% with respect to the NTSC standard, which is the same result as above.

Example 2 Red paste (R-3) in which the pigment / polymer ratio (weight ratio) of the non-photosensitive resin paste was 56/44 and green in which the pigment / polymer ratio (weight ratio) was 64/36. Paste (G-
3) and a blue paste (B-3) having a pigment / polymer ratio (weight ratio) of 39/61, and a photosensitive resin paste containing no pigment were used in the same manner as in Example 1. To produce a color filter.

The chromaticity (x, y) of the color filter thus obtained when passing through the C light source is red (0.675, 0.316) and green (0.201, 0.6), respectively.
82) and blue (0.145, 0.045), and the color reproduction range was 101.9% of the NTSC standard.

Using this color filter, a liquid crystal display device was completed in the same manner as in Example 1. The image quality of the obtained liquid crystal display device was capable of displaying vivid colors close to those of printed matter. The obtained display device was disassembled, the color filter with the alignment film was taken out, and the chromaticity of the color filter when it was passed through the C light source was measured in the same manner as above. ), Green (0.201, 0.6
82), blue (0.145, 0.045), and the color reproduction range was 101.9% with respect to the NTSC standard, which was the same result as above.

Example 3 A red paste (R-4) in which the pigment / polymer ratio (weight ratio) of the non-photosensitive resin paste was 65/35, and a green paste in which the pigment / polymer ratio (weight ratio) was 64/36. Paste (G-
3) and a blue paste (B-4) having a pigment / polymer ratio (weight ratio) of 50/50, and the red, green, and blue non-photosensitive resin pastes each have a thickness of 1.6 μm,
1.5 μm and 1.0 μm, the pigment / polymer ratio (weight ratio) of the photosensitive resin paste is 19/81 (G-4), and the photosensitive resin paste containing no pigment is red. , Example 1 except that they were laminated in a blue pattern
A color filter was produced in the same manner as in.

The chromaticity (x, y) of the color filter thus obtained when passing through the C light source is red (0.670, 0.320) and green (0.219, 0.6), respectively.
55) and blue (0.141, 0.064), and the color reproduction range was 92.5% of the NTSC standard. Using this color filter, a liquid crystal display device was completed in the same manner as in Example 1. The image quality of the obtained liquid crystal display device was capable of displaying vivid colors close to those of printed matter.

The obtained display device was disassembled, the color filter with the alignment film was taken out, and the chromaticity of the color filter when passing through the C light source was measured in the same manner as above.
Red (0.670, 0.320), green (0.219, 0.
655), blue (0.141, 0.064), and the color reproduction range was 92.5% of the NTSC standard, which was the same result as above.

Example 4 Pigment / polymer ratio (weight ratio) of a non-photosensitive resin paste on a glass substrate on which a black matrix was patterned
Of red paste (R-1) having a ratio of 49/51 is applied by a spinner so that the film thickness after heat treatment at 240 ° C. for 30 minutes is 3.3 μm, and dried in an oven at 120 ° C. for 20 minutes,
A positive photoresist (“OFPR-800” manufactured by Tokyo Ohka Co., Ltd.) was applied on this, and dried at 90 ° C. for 10 minutes. Canon Inc. UV exposure machine "PLA-50"
60m through a chrome photomask using 1F "
It was exposed to J / cm ² (ultraviolet intensity of 365 nm). After the exposure, it was immersed in a developing solution composed of a 2.25% aqueous solution of tetramethylammonium hydroxide to develop the photoresist and edging the colored coating film of polyamic acid at the same time. The photoresist layer that became unnecessary after etching was removed with acetone. The colored coating film of polyamic acid was heat-treated at 240 ° C. for 30 minutes to obtain a red pattern.

Next, the pigment / polymer ratio (weight ratio) is 64 /
The non-photosensitive green paste (G-3), which is No. 36, was applied by a spinner so that the film thickness after heat treatment at 240 ° C. for 30 minutes would be 1.5 μm, and the pigment / photosensitive resin paste pigment /
The film thickness of the green paste (G-4) having a polymer ratio (weight ratio) of 19/81 after heat treatment at 240 ° C. for 30 minutes is 1.
A green pattern was obtained in the same manner as in Example 1 except that the coating was performed with a spinner so that the thickness became 0 μm.

Next, the pigment / polymer ratio (weight ratio) is 18 /
82 non-photosensitive blue paste (B-5) is used and 2
A blue pattern was obtained by photolithography in the same manner as the red pattern except that the coating was carried out by a spinner so that the film thickness after heat treatment at 40 ° C. for 30 minutes was 2.8 μm.

The chromaticity (x, y) of the color filter thus obtained when passing through the C light source is red (0.670, 0.320) and green (0.219, 0.6), respectively.
55) and blue (0.141, 0.064), and the color reproduction range was 92.5% of the NTSC standard.

Using this color filter, a liquid crystal display device was completed in the same manner as in Example 1. The image quality of the obtained liquid crystal display device was capable of displaying vivid colors close to those of printed matter. The obtained display device was disassembled, a color filter with an alignment film was taken out, and the chromaticity of the color filter when it was passed through a C light source was measured in the same manner as above. ), Green (0.219, 0.6
55), blue (0.141, 0.064), and the color reproduction range was 92.5% of the NTSC standard, which was the same result as above.

Example 5 Red patterns and green patterns were formed in the same manner as in Example 1 on a glass substrate on which a black matrix was patterned. Next, a blue paste (B-6) having a pigment / polymer ratio (weight ratio) of 28/72 was used and applied by a spinner so that the film thickness after heat treatment at 240 ° C. for 30 minutes was 3.5 μm. A blue pattern was formed as in Example 4 except for the above.

The chromaticity (x, y) of the color filter thus obtained when passing through the C light source is red (0.675, 0.316) and green (0.201, 0.6), respectively.
82) and blue (0.145, 0.045), and the color reproduction range was 101.9% of the NTSC standard.

Using this color filter, a liquid crystal display device was completed in the same manner as in Example 1. The image quality of the obtained liquid crystal display device was capable of displaying vivid colors close to those of printed matter. The obtained display device was disassembled, the color filter with the alignment film was taken out, and the chromaticity of the color filter when it was passed through the C light source was measured in the same manner as above. ), Green (0.201, 0.6
82), blue (0.145, 0.045), and the color reproduction range was 101.9% of the NTSC standard.

COMPARATIVE EXAMPLE 1 A non-photosensitive red paste (R-1) prepared in D was prepared on a glass substrate on which a black matrix was patterned to give 240
After heat treatment at 30 ° C. for 30 minutes, a spinner was applied so that the film thickness would be 2.5 μm, followed by drying in an oven at 120 ° C. for 20 minutes, and then a positive photoresist (“OFPR-800” manufactured by Tokyo Ohka Co., Ltd. ") Was applied and dried at 90 ° C for 10 minutes. Canon Inc. UV exposure machine "PLA-5"
01F "through a chrome photomask 60
Exposure was performed with mJ / cm ² (ultraviolet intensity of 365 nm). After the exposure, it was immersed in a developing solution composed of a 2.25% aqueous solution of tetramethylammonium hydroxide to develop the photoresist and edging the colored coating film of polyamic acid at the same time. The photoresist layer that became unnecessary after etching was removed with acetone. The colored coating film of polyamic acid was heat-treated at 240 ° C. for 30 minutes to obtain a red pattern. Similarly, the non-photosensitive green paste (G-1) is applied by a spinner so that the film thickness after heat treatment at 240 ° C. for 30 minutes is 2.5 μm, and the green pattern is formed by photolithography in the same manner as the red pattern. Obtained. Next, non-photosensitive blue paste (B-1)
Is coated with a spinner so that the film thickness after heat treatment at 240 ° C for 30 minutes is 2.5 μm, dried in an oven at 120 ° C for 20 minutes, and photolithographically processed in the same manner as the red pattern to produce blue. Got the pattern.

The chromaticity (x, y) of the color filter thus obtained when passing through the C light source is red (0.668, 0.327) and green (0.205, 0.6), respectively.
85) and blue (0.144, 0.046), and the color reproduction range was 100.5% of the NTSC standard, but there was a crack in the green pattern in the screen, or there was a missing part, so it was defective. there were.

Comparative Example 2 A photosensitive red paste (R-5) having a pigment / polymer ratio (weight ratio) of 49/51 was prepared on a glass substrate on which a black matrix was patterned, and the mixture was prepared at 240 ° C. for 30 minutes. It was applied by a spinner so that the film thickness after the heat treatment of was 2.5 μm, and dried in an oven at 80 ° C. for 10 minutes. 100m through a chrome photomask using an ultraviolet exposure machine
It was exposed to J / cm ² (ultraviolet intensity of 365 nm). After the exposure, it was immersed in a developing solution composed of a 0.2% aqueous solution of tetramethylammonium hydroxide to edge the colored coating film of the photosensitive resin, and then rinsed with water. Further, the colored coating film of the photosensitive resin was heat treated at 240 ° C. for 30 minutes to obtain a red pattern. Next, a photosensitive green paste (G-5) having a pigment / polymer ratio (weight ratio) of 63/37.
And the film thickness after heat treatment at 240 ° C. for 30 minutes is 2.5
It was applied by a spinner so as to have a thickness of μm and dried in an oven at 80 ° C. for 10 minutes. Photolithography was performed in the same manner as the red pattern to obtain a green pattern. Next, a photosensitive blue paste (B-5) having a pigment / polymer ratio (weight ratio) of 35/65.
And the film thickness after heat treatment at 240 ° C. for 30 minutes is 2.5
It was applied by a spinner so as to have a thickness of μm and dried in an oven at 80 ° C. for 10 minutes. Photolithography was performed in the same manner as the red pattern to obtain a blue pattern.

The chromaticity (x, y) of the color filter thus obtained when passing through the C light source is partially red (0.668, 0.327) and green (0.20), respectively.
5, 0.685) and blue (0.144, 0.046), and the color reproduction range was 100.5% of the NTSC standard, but there were parts missing in the red and green patterns on the screen. The color reproduction range was partially defective because the color patterns were partially overlapped.

[0066]

As described above, according to the present invention, a color filter and a liquid crystal display device using the same can provide an excellent display having the same color vividness as a printed matter and no defects such as ITO disconnection.

[Brief description of drawings]

FIG. 1 is a configuration diagram of a color filter of the invention.

FIG. 2 is a block diagram of a conventional color filter.

[Explanation of symbols]

1: Glass plate 2: Black matrix 3: Colored film containing non-photosensitive resin 4: Colored film containing photosensitive resin 5: Overcoat 6: ITO

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA04 AB13 AD01 BC13 BC42                       CB25 CC11 DA31 FA35                 2H048 BA11 BA45 BA47 BA48 BB02                       BB44                 2H091 FA08Y FA41Z FB02 FB11                       FC26 FD06 LA12 LA16

Claims (9)

[Claims] 1. An area of a triangle connecting red, green, and blue chromaticity coordinates in an XYZ color system chromaticity diagram measured using a C light source is 80% or more of the NTSC standard, and one or more colors. The pixel is a color filter in which a layer containing a photosensitive resin is laminated on a colored layer containing a non-photosensitive resin. 2. The color filter according to claim 1, wherein the non-photosensitive resin is a polyimide resin and the photosensitive resin is an acrylic resin. 3. The color filter according to claim 1, wherein the film thickness of the photosensitive resin is not more than the film thickness of the non-photosensitive resin. 4. The film thickness of each pixel is 0.8 μm or more and 5
The color filter according to any one of claims 1 to 3, wherein the color filter has a thickness of not more than µm. 5. A chromaticity coordinate (x, y) in an XYZ color system chromaticity diagram measured using a C light source is 0.635 ≦ x.
The color filter according to any one of claims 1 to 4, wherein the color filter has a red pixel satisfying each of the formulas ≦ 0.680 and 0.300 ≦ y ≦ 0.350. 6. A chromaticity coordinate (x, y) in an XYZ color system chromaticity diagram measured using a C light source is 0.190 ≦ x.
The color filter according to any one of claims 1 to 4, wherein the color filter has a green pixel satisfying the respective expressions of ≤0.320 and 0.580≤y≤0.685. 7. The chromaticity coordinate (x, y) in the XYZ color system chromaticity diagram measured using a C light source is 0.130 ≦ x.
The color filter according to any one of claims 1 to 4, wherein the color filter has a blue pixel satisfying the respective expressions of ≤0.160 and 0.040≤y≤0.100. 8. A color filter in which an area of a triangle connecting red, green and blue chromaticity coordinates in an XYZ color system chromaticity diagram measured by using a C light source has an NTSC standard ratio of 80% or more. , After applying the color paste containing the uncured non-photosensitive resin, after applying the color paste containing the uncured photosensitive resin, the non-photosensitive resin and the photosensitive resin are simultaneously patterned by one photolithography process. A method for manufacturing a color filter for a liquid crystal display device, comprising: 9. A liquid crystal display device using the color filter according to claim 1.