JPH0263204B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method of manufacturing a color filter.
A color filter layer with a certain set of colors such as red, green, blue, yellow, cyan, and magenta is formed in a striped or matrix-like fine pattern on a transparent substrate such as glass or a solid-state image sensor plate. The present invention relates to a method of manufacturing a color filter that is built into a video camera and used to convert a color image signal into an electrical signal.

(Prior Art to the Invention) Conventionally, in order to make a dyeable resin layer, for example, a resin layer that is easily dyed and made of gelatin, grue, low molecular weight gelatin, etc. into a filter, the Japanese Patent Publication No. 52-
As described in Japanese Patent No. 17376, a dye-resistant resist film was formed with openings only in the areas to be dyed, and the easily dyed resin layer was immersed in a dye solution to be colored. However, this method has a problem in that the dye contained in the filter layer diffuses over time and mixes colors with adjacent filter layers of other hues. Some proposals have been made to provide a resist dyeing layer or an intervening layer between the filter layers, but these methods have the problems of increasing the number of steps and making it difficult to obtain a filter layer with high image precision.

(Object of the Invention) The present invention has been made in view of the above circumstances, and its purpose is to provide a method for manufacturing a color filter that does not cause color mixing between adjacent color filter patterns and has a high pattern accuracy. There is something to do.

(Summary of the Invention) That is, the present invention provides a dyeable thin film formed on a substrate, which is modified into a non-dyeable thin film by the presence of a dyeing inhibitor that decomposes when irradiated with ultraviolet rays. In contrast, (a) a step of partially replacing the non-staining thin film with a dyeing thin film by irradiating a desired portion of the non-staining thin film with ultraviolet rays to decompose the dyeing inhibitor; (b) partially replacing the non-staining thin film with a dyeable thin film; (c) a step of fixing the dye in the filter layer by adsorbing a dye fixing agent to the filter layer; This method of manufacturing a color filter is characterized in that steps (a) to (c) are repeated for the required number of colors.

(Detailed Description of the Invention) The color filter according to the manufacturing method of the present invention may be formed on a transparent substrate such as a glass plate, or may be formed on a solid-state image sensor plate with a transparent smooth layer or the like interposed therebetween. There are cases. The dyeable thin film used in either case is a thin film made of a substance that is easily stained by dyes such as direct dyes, basic dyes, acid dyes, etc. Specifically, the dyeable thin film used is a thin film made of a substance that is easily stained by dyes such as direct dyes, basic dyes, acid dyes, etc. It is preferable to use a water-soluble photosensitive resin using dichromate as a crosslinking agent. When such a photosensitive resin liquid is applied onto a substrate, dried, and then exposed to light, it hardens and becomes water-insoluble, and can be colored by immersing it in a dye solution.

Anti-staining agents are decomposed by ultraviolet light (actually, it is often far ultraviolet light).
Organic resist dyes such as tannic acid, formalin, and phenol can be applied. These stain inhibitors can be decomposed by irradiation with far ultraviolet rays having a wavelength of about 180 nm to 365 nm.

This dyeing inhibitor is present in the dyeable thin film to form a non-stainable thin film. One method for this is to apply and form a non-stainable thin film on the substrate, and then bring a staining inhibitor solution into contact with the thin film so that it is adsorbed onto the dyeable thin film.Another method is to form a dyeable thin film. It is added in advance to a photosensitive resin solution for dyeing, and then applied to form a non-dyeable thin film. Regarding the method of partially irradiating ultraviolet rays, since the key point is to irradiate the areas partially, a substance that blocks the ultraviolet rays except for the desired areas is interposed in a pattern between the ultraviolet light source and the dyeable thin film. Good.

Hereinafter, the steps of the present invention will be explained based on FIGS. 1 and 2 of the drawings. As shown in Figure 1A, a substrate 1 consisting of a glass transparent substrate, a solid-state image sensor plate, etc.
A stainable thin film 2 is formed by adding a staining inhibitor thereon and modifying it into a non-dying thin film. On the other hand, as shown in FIG. 1B, a quartz mask 3 is placed in close contact and ultraviolet rays 4 are partially irradiated. The quartz mask 3 has a transparent substrate 5 made of quartz glass with high ultraviolet transmittance, and a light-shielding layer 6 made of metal or a metal compound is partially provided on one side of the substrate. It is possible to selectively expose ultraviolet rays only to the areas desired to be dyed with the first color. In this way, as shown in FIG. 1C, the portion 2a irradiated with ultraviolet rays becomes a dyeable area as the dyeing inhibitor decomposes. Subsequently, if dyeing is carried out by immersion in a dyeing solution, the portion 2b where the stain inhibitor is present will not be dyed, and the portion 2a that has been irradiated with ultraviolet rays will be dyed.
Only the filter layer 7a is dyed to form the first color filter layer 7a. Thereafter, a solution of a dye fixing agent is brought into contact with the filter layer 7a to fix the dye on the filter layer 7a. By doing so, the dye in the filter layer 7a will not be eluted in subsequent steps, and will prevent other dyes from newly dyeing the filter layer 7a (see FIG. 1D).

FIG. 1E shows a process for creating a second color filter layer, and this state corresponds to FIG. 1B described above in the first color process. However, in FIG. 1E, a quartz mask is applied so that the irradiation area does not overlap with the already created filter layer 7a, and ultraviolet rays are irradiated to create the second color filter area. This process is repeated until the required number of colors for the filter layer is satisfied.

FIG. 2 shows another embodiment of the present invention,
To explain this, as shown in FIG. 2A, a dyeable thin film 2 serving as a filter layer on a substrate 1 is impregnated with or mixed with an anti-staining agent, and a UV-absorbing photosensitive resin film 8 is placed on top of it. Evenly coat and form. Since most photosensitive resins are sensitive to and absorb ultraviolet light, they can be used in the present invention. If necessary, a photosensitive resin may be mixed with an ultraviolet absorber. As shown in FIG. 2B, the photosensitive resin film 8 is partially irradiated and developed using a known photolithography technique to form a pattern, so that the portion to be irradiated with ultraviolet rays is formed into an opening. The photosensitive resin film 8' is rated at 9. After that, ultraviolet light 4 is irradiated from above.
At this time, the photosensitive resin film 8' partially blocks the ultraviolet rays 4 in the same manner as the quartz mask 3 described above, and only the portion 2a irradiated with ultraviolet rays becomes a dyeable area (see Fig. 2C). ). Then, if you immerse it in a dye solution,
Part 2 irradiated with ultraviolet rays as shown in Figure 2 D
Only layer a is colored, forming the first color filter layer 7a.

After dyeing, the filter layer 7a is fixed, the photosensitive resin film 8' is dissolved and removed, and the second
The state shown in the figure (E) and the filter layer 7a of the first color.
The forming process is completed.

Subsequently, as shown in FIG. 2F, in order to form a second color filter layer, a portion of the dyeable thin film 2b that will become the second color filter layer is partially irradiated with ultraviolet rays. For this purpose, a new photosensitive resin film 8'' is created with openings at the locations that will become the second color filter layer.
until the required number of filter layer colors is met.
This process is repeated.

(Example 1) A color filter was created according to an example of the present invention shown in FIGS. 1A to 1E.

A water-soluble photosensitive material shown below was applied onto a glass substrate by spin coating, dried and cured, and a dyeable thin film having a thickness of 1.2 μm was formed by exposing the entire surface to light.

Low molecular weight gelatin...15 parts by weight (average molecular weight approx. 20,000) Ammonium dichromate...2 parts by weight Water...85 parts by weight Next, soak in a 1% by weight tannic acid aqueous solution heated to 50-60℃ for about 1 minute. By dipping, tannic acid is adsorbed into the dyeable thin film to form a non-dyeable thin film.
This tannic acid aqueous solution is a polyhydric phenol and has good adsorption to dyeable thin films such as gelatin.

Next, a quartz mask with an opening in the desired area is interposed, and the irradiation time is 30 seconds or more at a distance of 5 cm from the U-shaped far ultraviolet lamp, as shown in Figure 1 (b).
It was irradiated for 1 minute to oxidize and decompose the tannic acid in the non-stainable thin film corresponding to the exposed area to create a dyeable area.

Subsequently, it was immersed in the staining solution shown below for about 3 minutes to create a red filter layer.

Kayanol Milling Red RS...10g (manufactured by Nippon Kayaku Co., Ltd.) Acetic acid...10c.c. Water...1000c.c. Solution temperature...60℃ After dyeing, use the following dye fixing solution (1), (2) 50 each
Elution of the dye was prevented by dipping for a second (see Figure 1D).

Fixer (1) (liquid temperature 50-60℃) Tannic acid ...0.5 parts by weight Acetic acid ...1.0 parts by weight Water ...98.5 parts by weight Fixer (2) (liquid temperature 60℃) Potassium antimonyl tartrate ...1.0 Parts by weight Water: 99 parts by weight To form color filter layers of second and subsequent colors, the above steps were repeated. For reference, the composition of the dye solution and dyeing conditions for forming the green filter layer and the blue filter layer are shown.

(Green staining solution) Suminol Milling Brilliant Green
5G...3g (manufactured by Sumitomo Chemical Co., Ltd.) Acetic acid 10c.c. Water 1000c.c. Solution temperature 60℃ Immersion time 3 minutes (blue staining solution) Kayanol Cyanine G 6g (manufactured by Nippon Kayaku Co., Ltd.) Acetic acid 5c.c. Water 1000c.c. Liquid temperature 50°C Immersion time 2 minutes [Example 2] An example of the present invention shown in FIGS. 2A to 2F of the drawings will be described below. As shown in Figure 2A, a dyeable thin film is coated and formed on a glass substrate, and immersed in a 1% by weight tannic acid solution at a temperature of 50 to 60°C for about 1 minute. Adsorbs acids and provides non-staining properties.

Next, photosensitive resin for masks (for example, positive type
AZ-1350) on the entire surface as shown in Figure 2 B.
A desired pattern is formed as shown in FIG. 2C by exposure and development using known means, and deep ultraviolet rays are irradiated thereon to oxidize and decompose the dyeable thin film exposed by patterning to impart dyeability. After dyeing to a desired color as shown in FIG. 2D by a conventional method, a dye fixing solution is adsorbed in the same manner as in Example 1 to impart non-staining properties. Thereafter, the masking resist remaining on the surface is peeled off to complete the formation of the first color color filter layer.

To form the color filter layers of the second and subsequent colors, a large number of sets of filter layers can be formed by repeating the steps from A to E in FIG.

(Effects of the Invention) As described above, the present invention modifies the dyeable thin film to be non-stainable by adding a dye-inhibiting agent such as tannic acid, and irradiates a desired area with ultraviolet rays to dye only that area. Since it converts into color, when dyeing with a dye solution, the dye does not stick to adjacent areas that do not want to be dyed. In addition, since the filter layer after dyeing is subjected to a dye fixing process, color mixing due to the diffusion of dye between the color filter layers is prevented even with subsequent changes over time.

Furthermore, since the dyeable region is created using short wavelength light from ultraviolet to far ultraviolet light, there is little light diffraction, and extremely high-density and precise color filter pattern accuracy can be achieved.

[Brief explanation of drawings]

1A to 1H are schematic sectional views showing one embodiment of the method for manufacturing a color filter of the present invention in the order of steps, and FIGS. 2A to 2F are schematic sectional views showing another embodiment of the present invention in the order of steps It is a diagram. DESCRIPTION OF SYMBOLS 1...Substrate, 2...Dyeable thin film, 3...Quartz mask, 4...Ultraviolet light, 5...Transparent substrate, 6...Light shielding layer, 7...Filter layer, 8...Photosensitive resin film,
9...Opening.

Claims (1)

[Claims] 1. For a dyeable thin film formed on a substrate, which has been modified into a non-dyeable thin film by the presence of an anti-staining agent that decomposes when irradiated with ultraviolet rays, ( a) partially replacing said non-staining thin film with a dyeing thin film by irradiating a desired portion of said non-staining thin film with ultraviolet rays to decompose the dyeing inhibitor; (b) partially converted dyeing; (c) a step of fixing the dye of the filter layer by adsorbing a dye fixing agent to the filter layer; the above step (a); A method for manufacturing a color filter, characterized by repeating steps (c) for the required number of colors. 2. The method of manufacturing a color filter according to claim 1, wherein the substrate is a transparent substrate made of glass. 3. The method of manufacturing a color filter according to claim 1, wherein the substrate is a solid-state image sensor plate. 4. The method for manufacturing a color filter according to claim 1, wherein the desired portion of the non-stainable thin film is irradiated with ultraviolet rays through a quartz mask. 5. When irradiating a desired part of a non-staining thin film with ultraviolet rays, a UV-absorbing photosensitive resin film is formed on the non-staining thin film except for the irradiated part, and then irradiated with ultraviolet rays. Color filter manufacturing method. 6. The method for manufacturing a color filter according to claim 1, wherein the irradiated ultraviolet rays are deep ultraviolet rays with a wavelength of 180 to 365 nm.