JPH0242405A - Production of color filter - Google Patents

Abstract

PURPOSE:To allow dyeing in a short period of time with a thin film thickness and to form fine dyed patterns with high accuracy without using surplus equipment by using a specific photosensitive resin for dyeing to a dye element colored layer. CONSTITUTION:The photosensitive resin prepd. by adding a water soluble bis- azide compd. as a crosslinking agent to the three-dimensional polymer of a compd. having the structure of N-vinyl-2-pyrrolidinone and quaternary amine and having a polymerizable unsatd. bond and the compd. having the structure expressed by the formula I is applied on a substrate. The resin is selectively exposed and is developed with water to form the patterns of the resin. The patterns are dyed to form dyed patterns. In the formula, R1 denotes H, CH3; R2 denotes CnH2n+1(n1-8). The color filter is obtd. with the thin film thickness under the dyeing conditions of the temp. near room temp. and the short period of time in this way; in addition, the resolving power increases and the pattern registration is facilitated. The development with water is possible and environmental pollution does not arise.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a color filter.
Applications include color video cameras and other color filters that recognize and separate light.

For example, a conventional color filter is used by arranging color elements in a mosaic or stripe pattern on a light-receiving element surface of a solid-state image sensor for colorizing a color television camera using a solid-state image sensor.

The color elements commonly used are blue, red, and green. Photosensitive resins with dyeing properties used in conventional color filters include photosensitive resins in which a dichromate such as ammonium dichromate or potassium dichromate is added as a photocrosslinking agent to proteins such as gelatin or casein. There is a composition. The general manufacturing method for color filters is to apply dichromate-added gelatin or casein onto a glass plate using the spin code method, and then irradiate it with ultraviolet rays through a mask to form a latent image of the color element dyed layer. Then, the color element dyed layer is exposed by development. Next, the color element dyed layer is dyed with a dye. red,
In order to form the blue and green color element dyed layers, the above steps are repeated 3 times while forming an optically transparent intermediate film to prevent mixed dyeing.
This process is repeated several times to form a color filter.

Problems to be Solved by the Invention The performances required of the dyeable photosensitive resin used in color filters manufactured through the above-mentioned processes are (1) good resolution; (2) dyeing properties; (3) good storage stability; and (4) no risk of causing environmental pollution to the photosensitive resin and developer. Photosensitive resins made from casein and gelatin, which are currently widely used, show almost satisfactory performance in terms of resolution, but because alkali is used to increase solubility in water, dark reactions cause dark Hydrolysis of the resin also progresses in places, gradually changing its quality and making it unusable. Furthermore, since it contains a dichromate such as ammonium dichromate as a photocrosslinking agent, drainage equipment is required for disposal. Furthermore, regarding stainability,
It largely depends on the film thickness, and requires high temperature and long-term image pH as staining conditions.

As the thickness of the resin film increases, not only does the amount of ultraviolet rays (exposure amount) required to cure the resin increase, but also because light is irradiated through diffraction to areas where light is blocked by the mask. Resolution decreases. Therefore, the film thickness of the resin is required to be as thin as possible. Therefore, the dyeability of the resin used in the color element dyeing layer must be such that it can achieve a dyeing concentration sufficient to obtain the necessary spectral characteristics with a thin film thickness, and at low temperatures and in a short period of time. .

Therefore, resins that require a film thickness of 0.8 μm or more, such as casein and gelatin, are inappropriate. The present invention provides a method for manufacturing a color filter in which a photosensitive resin for dyeing with high resolution, which can be dyed at around pH neutrality and in a short time, is used in a colored layer of a color element.

That is, the present invention provides N-vinyl-2-pyrrolidinone and 4
Using N-vinyl-2-pyrrolidinone, a monomer having a class amine structure and a polymerizable unsaturated bond, and a compound having the structure shown below, the compound has a dyeing function. , a compound having a quaternary amine structure and a polymerizable unsaturated bond was used. Further, in order to adjust the water solubility, a hydrophobic compound having the following structural formula was used.

A photosensitive resin made by adding a water-soluble bisazide compound as a crosslinking agent to a binary copolymer of is applied onto a substrate, selectively exposed to light, developed with water to form a resin pattern, and this pattern is dyed. This is a method for forming color filters.

Function: The photosensitive resin for dyeing used in the present invention has been designed according to the following molecular design. That is, it has a structure formed by ternary copolymerization of a compound having a photosensitive function, a compound having a dyeing function (around neutral pH), and a compound having a function of adjusting water solubility. Specifically, the photosensitive compound is a water-soluble compound that easily reacts with the crosslinking agent when exposed to ultraviolet rays.By using such a resin, dyeing can be done in a short time with a thin film thickness, and redundant equipment is required. It becomes possible to obtain a color filter having a highly accurate fine dyeing pattern without using.

Examples Compounds having the structure of a quaternary amine and having a polymerizable unsaturated bond include: (1) 2-hydroxy-3-methacryloxyprobyltrimethylammonium chloride (2) 4.45 diazidostilbene-2,2' Examples include sodium sulfonate dimethacryloyloxyethyltrimethylammonium chloride. Next, hydrophobic compounds that adjust water solubility include methyl methacrylate, ethyl methacrylate,
Examples include propyl methacrylate, isopropyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and the like. Water-soluble and dyeable photosensitive resins made by copolymerizing the three types of compounds mentioned above are extremely stable, and even those with crosslinking agents can withstand storage for more than three months if stored in the dark. can. As a crosslinking agent that reacts with ultraviolet light, ■ 2,6-
Pis + 4'-azidobenzal + 4 = methylcyclohexanone-2,2'-sodium disulfonate ■ 1,3-bis + 4'-diazobenzal + 2propanone-sodium 2,2'-disulfonate ■ 2.6-pis + 4'-azidobenzal ÷Cyclohexanone-2,2
'-Sodium disulfonate S O3Ha
Examples include S O3N 2L.

If the molar ratio of N-vinyl-2-pyrrolidinone contained in the resin is less than 30%, photosensitivity will be low, and casein and gelatin-
Photosensitivity is inferior to dichromate type. Furthermore, if the molar ratio of the compound having a quaternary amine structure is less than 6%, the dyeing property is poor and the necessary optical density cannot be obtained with a film thickness of 0.sup.7zm or less.

If it exceeds 30%, the solubility in water is high and the film tends to become rough. If the molar ratio of the hydrophobic compound for adjusting the solubility in water exceeds 60%, the solubility in water will drop significantly and development in water will become impossible, so this range is desirable.

Further, if the molar ratio is less than 10%, the solubility is high and development with water becomes difficult. Therefore, the composition of the resin of the present invention jfJj,
The molar ratio of N-vinyl-2-pyrrolidinone is 30%-8
6%, the molar ratio of a compound having a quaternary amine structure and a polymerizable unsaturated bond is 5% to 30%, and the molar ratio of a compound for adjusting the solubility in water is 10% to 6.
0% is desirable.

Since the resin used in the present invention is a terpolymer of each element, the required performance can be brought out by changing the composition ratio depending on the application.

When this photosensitive resin is applied onto a glass plate, irradiated with ultraviolet rays, and then dyed to produce a color filter, it has the following advantages compared to gelatin or casein-dichromate based photosensitive resins. ing.

(1) The same optical density can be achieved with a thinner film thickness compared to gelatin or casein-dichromate photosensitive resins. Table 1 shows the results.

(Margins below) Table 1 Table 2 (2) Gelatin or casein-dichromate photosensitive resins have the same area to be dyed and the area where photocrosslinking occurs, so they cannot be dyed by light irradiation. part changes. However, in the resin used in the present invention, the parts exhibiting each function are independent from each other, so the dyeing is not affected by light irradiation. The second table is
It shows the change in film thickness to obtain the same optical density when the amount of light irradiation changes.

(Margin below) As can be seen from the above results, the resin used in the present invention can obtain the same optical density with a film thickness of 0% to 30% compared to conventional resins, and therefore the light intensity during light irradiation is Resolution is improved with less influence from diffraction. Furthermore, staining can be carried out at room temperature in a short time.

Next, examples of dyes capable of dyeing this photosensitive resin will be given.

(1) Red dyes include Suminol Milling Scarlet G (Sumitomo Chemical) and Cibacron Scarlet ep (Ciba Geigy).

Cibacron Pronto Scarlet (Ciba Geigy), Suminol Fast Red G (Sumitomo Chemical)
, Sumilite Splat Red 4BL (Sumitomo Chemical)
, Aminyl Red E-2BL (Sumitomo Chemical), Aminyl Red E-3BL (Sumitomo Chemical), Azide Scarlet 901 (Sumitomo Chemical), Suminol Milling Scarlet FC (Sumitomo Chemical), Suminol Milling・Orange SG (Sumitomo Chemical), Suminol Fast Orange PO (Sumitomo Chemical).

Maxilon Red GRL (Chiba Gaikie).

Eriosin Scarlet RE (Chipa Geigy)
, Mikawan Brilliant Red aBs (Mitsubishi Chemical), Acid Light Scarlet GL130% (Mitsubishi Chemical), Kayanol Milling Red R3125 (
Mitsubishi Chemical), etc.

(2) As green dyes, Suminol, Milling,
Brilliant Green sG (Sumitomo Chemical).

Acid Brilliant Milling Green G (Sumitomo Chemical), Acid Brilliant Milling Green B
(Sumitomo Chemical), Mication Olive Green 3G
S (Chiba Geikie).

Kayanol Milling Green 6GW (Nippon Kayaku), Sooriidazole Green PGG (Hoechst)
, Paper Fast Green 5G (Pyhel), etc.

(3) Blue dyes include Sumilite Sublar Turquoise Blue G (Sumitomo Chemical) and Cibacuron Blue 3G-A (Ciba Gaikie).

Chidochlorane Blue 8G (Ciba Gaikie).

Prodione Turquoise H-A (CIO).

Kayachi Onturquois P-A (Nippon Kayaku).

Kayathion Turquoise P-NGF (Nippon Kayaku).

Sumikalon Blue E-FBL (Sumitomo Chemical).

Sumikalon Brilliant Blue 5-BL (Sumitomo Chemical), Suminol Leveling Sky Blue R Extra Conc (Sumitomo Chemical).

Orazole Blue GN (Ciba Gaikie).

Makidion Blue sGs (Mitsubishi Chemical), Makidion Blue 2GS (Mitsubishi Chemical), Kayanol Milling Blue GW (Nippon Kayaku).

Examples include Kayaburu Sky Blue R (Nippon Kayaku).

Next, more detailed examples of the resin used in the present invention will be described.

N-vinyl-2-pyrrolidinone 30.09
Propyltrimethylammonium chloride Methyl methacrylate 15.0p Azobisisobutyronitrile 0.2g Methanol 260ml The liquid of the above formulation was placed in a three-necked flask, and after purging the reaction vessel with nitrogen for 1 hour, the temperature was raised to 66°C. Polymerization was carried out while stirring for 6 hours. After the polymerization was completed, the mixture was precipitated in a large amount of ethyl acetate, washed with petroleum ether, and then dried under reduced pressure to remove the solvent. 4. After drying, dissolve in water and use as a crosslinking agent.
A photosensitive resin solution was prepared by adding 6q of sodium 4'-diazidostilbene-2,2'-disulfonate to 1y of resin.

FIGS. 1 to 3 are cross-sectional views showing each step of an embodiment of the present invention for forming a color separation filter for a solid-state image sensor.

The photosensitive resin solution described above is uniformly applied onto the transparent substrate 1 using a spinner. Next, ultraviolet rays were irradiated through a mask (surface illuminance 4.6 MW/aIIX 6 seconds) to form a latent image of pattern part 2 of the first color, which is the part that should feel red, and this was developed with water at 26°C for 30 seconds. It was brought to light. Next, pattern portion 2 was dyed under the following conditions.

Suminol Milling Red G 1.0wt
% acetic acid 2.0 wt % pure water A transparent intermediate film (methyl methacrylate polymer) 3 is similarly applied using a spinner on the upper part of the pattern section 2 dyed at a dyeing temperature of 26° C. for 4 minutes. FIG. 1 is a sectional view showing this state.

Next, the photosensitive resin solution is uniformly applied again and exposed through a mask in the same manner as the first color to form a latent image of the pattern portion 4 of the second color, which is the portion that should feel green.
Developed with water at 6° C. for 30 seconds. Thereafter, the pattern portion 4 was dyed under the following conditions.

Suminol Milling Brilliant Green 6G2
．． 0wt% acetic acid 2. Owt% pure water dyeing temperature, time: 26° C., 6 ml The above-mentioned transparent intermediate film 6 was applied on top of this film. Second
The figure is a sectional view showing this state.

Further, the above photosensitive resin solution was uniformly applied on the upper part, exposed and developed in the same manner as the first and second colors to form a third color pattern part 6, which is a part that should feel blue. Next, this pattern portion 6 was dyed under the following conditions.

Cibachloran Shima Blue-8G 1.0wt
% Acetic acid 2.0wt
% pure water dyeing temperature and time 26° C. for 6 minutes to form a top coat 7 on top of this to obtain a color separation filter shown in FIG. A mosaic color separation filter for a solid-state imaging device can be formed by the above method.

FIG. 4 shows a one-color separation filter formed directly on a solid-state image sensor 9 made of a semiconductor substrate or the like using the above method, and the same parts as in FIG. 3 are given the same numbers. Reference numeral 8 indicates a light detection section of the solid-state image sensor 9.

Effects of the Invention The present invention provides a method for manufacturing a color filter in which a monomer having a structure of N-vinyl-2-pyrrolidinone and a quaternary amine and having a polymerizable unsaturated bond and the following monomers are used in a colored layer of a color element. By using a photosensitive resin composition made by adding a water-soluble bisazide compound to a terpolymer of a compound having such a structure, conventional casein and gelatin-
Compared to dichromate-based photosensitive resins, it is possible to obtain a filter with a thin film thickness of 30% to 60% and the same optical density under dyeing conditions of short time around room temperature. Furthermore, since the required optical density can be obtained with a thin film thickness, the resolution is increased and pattern alignment is facilitated, and at the same time it can be developed with water and does not cause environmental pollution. Furthermore, by changing the ratio of the three types of compounds, the film thickness, dyeing concentration, dyeing conditions, etc. can be selected depending on the application.

In this manner, the present invention greatly contributes to the mass production of color filters having highly accurate fine m 2 patterns.

[Brief explanation of the drawing]

1, 2, and 3 are cross-sectional views showing the manufacturing process of a color filter according to an embodiment of the present invention, and FIG. 4 is a cross-sectional view of a solid-state imaging device using the color filter according to the present invention. . 1... Substrate, 2... First color pattern, 3... Intermediate film, 4... Second color pattern, 6... ...intermediate film, 6...3rd
Color pattern, 7...Top coat, 8...
. . . Photodetection section, 9 . . . Solid-state image sensor.

Claims (1)

[Scope of Claims] A monomer having the structure of N-vinyl-2-pyrrolidinone and a quaternary amine and having a polymerizable unsaturated bond, and a compound having the following structure ▲ Numerical formula, chemical formula, table A process of applying a photosensitive resin made by adding a water-soluble bisazide compound as a crosslinking agent to a terpolymer of ▼ onto a substrate, and forming a pattern on the resin by selectively exposing the resin and developing with water. A method for producing a color filter, comprising the steps of: forming a color filter; and dyeing the formed pattern to form a dyed pattern.