JP3274245B2 - Manufacturing method of color filter - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter suitably used for fine color separation of a color sensor, a color solid-state imaging device, a color display and the like.

[0002]

2. Description of the Related Art Conventionally, a method of producing a color filter using a colored resin in which a dye is dispersed or dissolved in a transparent resin (hereinafter, abbreviated as a dye dispersion method) is disclosed in Japanese Patent Application Laid-Open No. 55-115003.
JP, JP-A-57-16407, JP-A-57-74707, JP-A-61-77804, JP-T-1-501973, JP-A-Hei.
It is known from JP-A-2-127602. For example, when the resin is non-photosensitive, a method of forming a patterned colored resin film by printing on a substrate, or after forming a colored resin film,
There is a method in which a mask made of a resist is provided on the colored resin film and patterning is performed by etching. When the resin is photosensitive, a patterned colored resin film is formed by using a photolithography process.

In the dye dispersion method, the selection of the dye is an important point that determines the characteristics of the color filter. The properties required for such dyes include: solubility or dispersibility in resin sufficient to obtain the required spectral characteristics, spectral characteristics that meet the specifications as color filters, heat resistance that satisfies the device fabrication process and device quality requirements. (Especially S
In the case of a TN type color display, about 250 ° C. is used for imidizing a polyimide precursor used as an alignment film.
To a certain extent), light resistance, chemical resistance, and storage stability when a dye is dispersed in a resin. However, a color filter using a dye that satisfies all of these necessary properties has not been known yet, and therefore, the use of the conventional color filter is limited by its properties, and the usable range is narrow. I was

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned disadvantages of the prior art, and to improve the spectral characteristics, heat resistance, and the like.
An object of the present invention is to provide a color filter which is excellent in light resistance and chemical resistance, and has excellent storage stability of a dye-containing resin solution used and excellent solubility or dispersibility of a dye in the solution.

[0005]

Generally, it is difficult to theoretically and reliably predict the properties of a dye and a composition in which the dye is dispersed from the structural formula and composition of the component. It relies heavily on the rules of thumb and experiments of those skilled in the art. In view of the above problems, the present inventor has conducted tests and studies on a wide range of dyes one by one for dyes that can be used in color filters, regardless of dyes that have been conventionally used. Was. As a result, it has been found that the above problems of the color filter can be solved by using a specific dye.

That is, the color filter of the present invention comprises a substrate, and a dye-containing resin composition film formed in a pattern on the substrate. I. Solven
t Red 35, C.I. I. Solvent Red
83, C.I. I. Solvent Red 89, C.I. I.
Solvent Red 138, C.I. I. Solve
nt Red 160, C.I. I. Solvent Re
d 218, C.I. I. Solvent Red 23
0, C.I. I. Acid Red 151, C.I. I. So
lvent Blue 78, C.I. I. Solvent
Blue 94, C.I. I. Solvent Blue
68, C.I. I. Disperse Blue 19
8, C.I. I. Solvent Yellow 62,
C. I. Solvent Yellow 93, C.I.
I. Solvent Yellow 104, C.I. I.
Solvent Yellow 105, C.I. I. So
lventYellow 114, C.I. I. Solve
nt Yellow 129, C.I. I. Solvent
Yellow 130, C.I. I. Solvent Y
yellow 162, C.I. I. Disperse Ye
llow 201, C.I. I. Solvent Oran
ge 11, C.I. I. Solvent Orange
37, C.I. I. Solvent Orange 62,
C. I. Solvent Orange 99, C.I.
I. Solvent Violet 33, C.I. I. S
solvent violet 45, and C.I. I. So
livnt Violet 46.

Hereinafter, the present invention will be described in detail. As the resin used in the present invention, polyimide, polyamide imide, polyester imide, polyamide, polyester,
It can be arbitrarily selected from polystyrene, polyparaxylene, melamine resin, acrylic resin, epoxy resin, polysilicon resin, resins obtained by imparting photosensitivity to these resins, and general photoresist resins. Preferably, a polyimide resin, a polyamide resin, or an acrylic resin is used in consideration of transparency, heat resistance, light resistance, and pattern processability, which are required characteristics of a color filter.

The dye may be used alone. However, when the dye is usually red, the red dye is combined with Yellow and / or Orange.
mixture of e-dye, blue for blue and yellow
And / or a mixture of Orange dyes, B for blue
A mixture of lue dye and Red dye and / or Violet dye can be used. The dye is used in an amount of 10 to 150% by weight, preferably 20 to 60% by weight, based on the resin.
It is.

As the method for forming the dye-containing resin layer of the color filter according to the present invention, there are a forming method by printing such as screen, gravure, offset, intaglio offset, a forming method by ink jet, and a forming by etching using a positive resist mask. In the case of a photosensitive resin, a method of forming a pattern by photolithography after coating on a substrate by a coating device such as a spinner, a roll coater, a bar coater, or a dip may be used.

The thickness of the color filter is usually 0.5 to 5 μm.
m, preferably about 1-2 μm. When it is necessary to enhance the adhesiveness between the dye-containing resin layer and the substrate, the substrate is preliminarily treated with a silane coupling agent or the like, or a colored resin to which a small amount of a silane coupling agent or the like is added is used. be able to.

The color filter of the present invention has sufficient chemical resistance by itself. However, in order to further enhance the chemical resistance, an organic resin such as polyamide, polyimide, acrylic, epoxy, silicon, or Si ₃ O _{3 is used.} N ₄ , SiO ₂ , A
An inorganic film such as l ₂ O ₃ can be formed on the colored resin layer as a protective film.

[0012]

【Example】

Example 1 30 g of a copolymer of methacrylic acid and benzine methacrylate (molar ratio: 30:70, number average molecular weight: 20,000), 7 g of pentaerythritol tetraacrylate, 1.5 g of 2,2-diethoxyacetophenone, 0.02 g of hydroquinone monomethyl ether , Ethyl cellosolve acetate 6
5 g of a photosensitive resin solution was prepared. This photosensitive resin liquid was added with C.I. I. Solvent Red 8
9 6.0 g, C.I. I. Solvent Yellow
104 g was added and stirred to dissolve. The resulting solution was filtered through a 0.2 μm filter to obtain a dye-containing colored resin solution. This colored resin solution was applied on a glass substrate with a spinner and dried to obtain a colored resin film having a thickness of 2 μm. FIG. 1 is a sectional view of a color filter according to the present invention. As shown in FIG. 1, this color filter is formed by forming a colored resin film 2 on a substrate 1. After exposure using a mask with an ultra-high pressure mercury lamp under a nitrogen stream, development with a 2% aqueous solution of sodium carbonate, washing with water, and baking at 200 ° C. for 30 minutes to form a red pattern. The spectrum of the obtained red color filter is shown by a straight line a in FIG. As shown by the straight line a in FIG. 2, the obtained color filter has a transmittance of 75% or more at 610 nm and 2% or more at 570 nm. , The solubility of the dye was good. Next, the spectrum after heating this red color filter in an oven at 250 ° C. for 1 hour under a nitrogen stream is shown by a broken line b in FIG. When the color difference ΔE ^* ab was measured, the change was small and the heat resistance was good. This color difference △
E ^* ab is shown in Table 1. The color difference was measured after irradiating the red color filter with a sunshine carbon lamp for 100 hours, and it was found that the light resistance was good.
Table 1 shows the results. Further, an acrylic overcoat, Optmer SS6688 (trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.) was formed on the pattern at a thickness of 1 μm, and the chemical resistance was tested with isopropanol vapor. As a result, there was almost no change in the spectrum, and the chemical resistance was good.

When the colored resin solution was stored at 35 ° C. for 3 months, no dye was precipitated and the storage stability was good. Comparative Example 1 C.I. I. Solvent Red 89,
C. I. Solvent Yellow 104 instead of C.I. I. Solvent Red 8, C.I.
I. The test was performed in the same manner as in Example 1 except that Solvent Yellow 88 was used. The spectrum is shown in FIG. In FIG. 3, a solid line c indicates a spectral characteristic before heating, and a broken line d indicates spectral characteristics after heating.
These dyes have very poor heat resistance, and the spectrum greatly changes when heated at 250 ° C., which is not practical.
Similarly, when light resistance and chemical resistance were examined,
The spectral change after irradiation was large, and the dye exuded with isopropanol vapor. The dispersibility of the dye and the storage stability of the colored resin solution were satisfactory in the filtration of the photosensitive resin solution, and the dispersibility was good. However, precipitation of the dye was observed after storage for about 2 weeks, and storage stability was found to be insufficient.

As described above, the color filter obtained in Comparative Example 1 was excellent in dispersibility,
The light resistance, chemical resistance, and storage stability were insufficient.

Examples 2 to 19 Color filters were obtained in the same manner as in Example 1 except that the dyes having the compositions shown in Table 1 were used. The heat resistance and the light resistance were evaluated in the same manner as in Example 1. Table 1 shows the results. The chemical resistance, storage stability, and dispersibility were all good.

Comparative Example 2 C.I. I. Solvent Red 89, C.I.
I. Instead of Solvent Yellow 104,
C. I. Solvent Yellow 146, C.I.
I. A green photosensitive resin solution was prepared using Solvent Blue 38. The dispersibility of the dye was poor and only a small amount could be filtered. Spectroscopy, heat resistance, light resistance, and chemical resistance were poor, and the dye was deposited after storage for about one week.

[0017]

[Table 1]

[0018]

According to the present invention, the spectral characteristics of the filter,
A color filter having excellent heat resistance, light resistance, and chemical resistance, storage stability of a dye-containing resin solution to be used, and excellent solubility or dispersibility of a dye is provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of a color filter according to the present invention.

FIG. 2 is a graph showing spectral characteristics of an example of a color filter according to the present invention.

FIG. 3 is a graph showing spectral characteristics of an example of a conventional color filter.

Claims (3)

(57) [Claims] 1. A color filter comprising a substrate and a resin composition film containing a red dye mixture formed in a pattern on the substrate, wherein the red dye mixture comprises CISolvent Red 89 and CI
Combination with Solvent Yellow 104, CISolvent Red 138
With CISolvent Yellow 93, CISolvent R
Combination of ed 83 with CISolvent Yellow 104, CIS
olvent Red 160 with CISolvent Yellow 105, CISolvent Red 230 and CISolvent Yellow 11
Combination with 4, CISolvent Red 89 and CISolvent Yel
Combination with low 129, CIAcid Red 151 and CISol
Combination with vent Yellow 130, CISolvent Red 89
With CIAcid Red 151, CISolvent Red 8
9 with CISolvent Orange 11, CISolvent R
ed 89 in combination with CISolventOrange 37, CISol
combination of vent Red 89 and CISolvent Orange 62,
And CISolvent Red 89 and CISolvent Orange 99
A color filter selected from the group consisting of: 2. A color filter comprising a substrate and a resin composition film containing a green dye mixture formed in a pattern on the substrate, wherein the green dye mixture comprises CISolvent Blue 94 and C.I.
Combination with I. Disperse Yellow 201, CISolvent Blue
68 in combination with CISolvent Yellow 162, and C.I.
A color filter selected from the group consisting of a combination of I.Disperse Blue 198 and CISolvent Orange 11. 3. A color filter comprising a substrate and a resin composition film containing a blue dye mixture formed in a pattern on the substrate, wherein the blue dye mixture comprises CI Disperse Blue 198 and CI Disperse Blue 198.
Combination with CISolvent Violet33, CISolvent Blue
78 with CISolvent Red 35, CISolve
Combination of nt Blue 78 and CI Solvent Red 208, and CISolvent Blue 78 and CISolvent Violet
45. A color filter selected from the group consisting of: