JPS63220203A - color filter - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color filter. The details are related to the color filters used in color TVs.

[Conventional technology]

Conventionally, there are roughly two methods for manufacturing organic color filters.

First, the first manufacturing method involves coating an optically polished glass substrate with a photosensitive solution made by imparting photosensitivity to polyvinyl alcohol, greens, gelatin, casein, etc. with ammonium dichromate, etc., by roller coating or dipping. , spread it evenly with a spinner, etc., dry it, photo-cure only the seventh color pattern using a mask exposure method, and develop it to remove patterns other than the desired one to form a dyed base film.
7. Dyeing the base film with a dye having predetermined spectral characteristics.
Dye the color pattern. Next, a transparent resist film that cannot be dyed with dye is applied to the entire surface.

Next, the same photosensitive solution as above is applied uniformly in the same way, and after drying, it is exposed and photodeveloped by a mask exposure method to form a dyed base film of - color, and then a first dye having predetermined spectral characteristics is applied. dye with Furthermore, the transparent resist dyeing film is applied to the entire surface.

Using the same method, the same photosensitive solution as above is uniformly applied, dried, and then exposed and developed using a mask exposure method to form a dyed base film for the third color. Dye with dye.

Finally, a top coat is applied to produce the color filter.

However, in such a color filter method, when forming a dyed base film of a negative color, a dyed base film of a green color, and a dyed base film of a third color, the substrate conditions are different. That is, the dyed base film for the seventh color is formed directly on the glass substrate, but the dyed base film for the second color is formed directly on the glass substrate.
The dyeing base film of the third color is formed on the resist film of the seventh color, and the dye base film of the third color is formed on the resist film of the third color.

On the other hand, the adhesion of the photosensitive liquid differs between the glass substrate and the respective resist coatings. Therefore, due to the photosensitive material having good adhesion to a glass substrate, peeling is likely to occur at the interface of the resistive film when used, and such conventional methods of manufacturing color filters frequently result in poor peeling.

Furthermore, since there are anti-dye films in each case, /, ko, 3
There are steps in the dyed base film of color [j, = color,
Unravel the pattern as you form the third color! There were drawbacks such as the pattern of the dyeing paste film of the first, second, and third colors being blurred.

On the other hand, in the first manufacturing method, a light-shielding pattern is formed in a stripe shape on a light-transmitting glass substrate, such as Cr(
A metal layer is formed using a vapor-deposited film such as chromium). Here, the metal film is used as a light-shielding film to prevent optical noise from entering other than the photodiode portion of the solid-state image sensor.

Next, a dyeing paste film (hereinafter referred to as a resin film) is formed on the glass substrate to a thickness of 3 to 1 μm.

Next, on the resin film, a resist film such as a commercially available 7 otoresist is coated to a thickness of about 5oooλ using a spinner.
At 5℃! - Dry for 10 minutes.

Next, a glass plate having a mask with a predetermined pattern formed with emulsion or argon, etc. is placed on the photoresist, and the source is irradiated with a mercury lamp.

The exposed photoresist is then developed. As a result of development,
The exposed area is dissolved away, and an unexposed area, ie, an anti-dye film mask, and a dissolved area, ie, a non-masked area, are selectively formed. This dye-resistant film mask must be able to prevent dye from penetrating in the next process.

Next, the resin film selectively covered with the resist film mask is immersed in a dye, for example, Congo red, for yo-tio seconds to color the resin film red through the unmasked parts. Then, a red colored region is formed on the resin film.

Next, a photoresist coating is again formed on the resin film.

Then, a glass plate equipped with a mask having a pattern different from the aforementioned mask is placed on top of the photoresist, and the original is irradiated with a mercury lamp.

Next, by developing the exposed photoresist,
The exposed area is dissolved away, and the unexposed area is immediately immersed in a dye such as a mixture of Suminol Yellow and Patent Blue for 30 to 10 seconds to dye green through the unmasked area. Then, a green colored area is formed adjacent to the red colored area.

Next, a dye resist film mask and non-mask portions are formed in the same manner as above.

Then, the resin film selectively covered with this resistive film mask is immersed in a dye, for example, Diamond Blue, to form a stomach colored region. Thereafter, the resist film mask is removed to form a color filter, that is, a color filter having a red colored area, a green colored area, and a blue colored area.

However, in this first manufacturing method, it is possible to completely prevent the dye from spreading in the lateral direction during dyeing.
When the thickness exceeds .mu.m, color mixing with adjacent colors occurs, resulting in deterioration of optical characteristics as a filter.

In order to improve these drawbacks of the conventional method, JP-A-Sho! ;9-!
O'tt// has been proposed.

That is, the color separation area is colored black in advance to form a continuous light area, and then the entire surface is irradiated with heat rays, and the coloring base film in the black colored area, which has good absorption of heat rays, is baked and solidified to achieve highly polymerized color separation. A method for manufacturing a color filter has been proposed, which is characterized in that the colorant is prevented from spreading in the lateral direction beyond the color separation area in the subsequent coloring process.

[Problem that the invention seeks to solve]

However, the patent does not specifically describe a black dye for coloring the color separation area.

[Means for solving problems]

Therefore, the inventors of the present invention have conducted various studies on this point, and as a result, the dye has (1) sufficient dyeing power for gelatin, casein, etc.;

(2) In terms of spectral characteristics, it should have sufficient absorption in the range of 1.390 to 7 Q □ nm.

(3) Excellent robustness such as light resistance and heat resistance.

Basic performance is required, and for this purpose, the following general formula [I
] and [11) have been found to be excellent in meeting these requirements, leading to the present invention.

That is, the present invention is to provide a color filter containing a black dye, and its purpose is to provide a color filter having one or more colored layers, in which at least one of the colored layers has the following general formula [l] or [ID This is achieved by a color filter characterized by containing at least seven types of azo dyes shown in the following.

O (in the formula or a hydrogen atom, a lower alkyl group, or S 03M
represents a phenyl group which may be substituted with a group, m and n represent Q or /, M represents a hydrogen atom, an alkali metal, ammonium or amines, and A, B and C have a substituent. represents a benzene ring or naphthalene ring which may be

(In the formula, human and B represent a benzene ring or naphthalene ring which may have a substituent, m represents 0 or l, M
represents a hydrogen atom, an alkali metal, ammonium or amines) The present invention will be described in detail below.

The dye used in the present invention is selected from the following general formula [ID or [II].

O (in the formula, X represents a hydrogen atom, a lower alkyl group, or a phenyl group optionally substituted with an 803M group, m and I
n is 0 or /, M is a hydrogen atom, an alkali metal,
It represents ammonium or amines, and A, B, and O represent a benzene ring or a naphthalene ring which may have a substituent. ) (In the formula, human and B represent a benzene ring or naphthalene ring which may have a substituent, m represents O or /, and 1M represents a hydrogen atom or an alkali metal.

Further, as the dye of general formula CI), it is preferable to use dyes represented by the following general formulas (1111 to [V'), and as the dye of general formula Cm), it is preferable to use the dyes shown below. Those represented by the general formula [■] are preferable.

O (in the formula, Y and 2 represent a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, M, O.

X〆 and m have the same meaning as the above definition. )O (In the formula, A, M, X and m have the same meaning as the above definition.) O (In the formula, ! represents l or -, M, Y%
has the same meaning as the above definition. (In the formula, M, 1, and B have the same meanings as defined above.) Specific examples of the dyes used in the present invention include those shown in Tables 1 to 3.

The dye of the present invention can be prepared, for example, by Yutaka Hosoda, "New Dye Chemistry," Gihodo, 3rd page, line 7, lines 27 to 79g, line 9, etc. It can be produced by repeating diazotization and coupling.

Further, the color separation area can be colored black using the dye of the present invention based on the method described below.

That is, the dye of the present invention is applied to the light-shielding area forming part by 0.7 to /θ, 0%.
, preferably O93~-% aqueous solution, pH 3~g, preferably Guyo, temperature 30~IOθ℃, preferably 50~7
It can be colored by processing for 10 minutes in a dyeing bath adjusted by adding salt or the like at 0° C. to form a light-shielding area.

By using the dye of the disclosed invention, 79117-700
Although it is possible to sufficiently block light within the nff1 range, it is also effective to use the following dyes in combination in order to make it more complete.

0, X, Direct Yellow-g Ac1 engineering, Direct, Yellow-/q 2C0 engineering,
ACl (i Yellow-, 2ja, L Ac1
cL Orange-2gC1 Engineering, Ac1a Or
ange-II 3C, ■, Ac1d Orange
-/9C1■, Ac1d Green-, 2j [Example] The following examples demonstrate the present invention'? :I will explain in more detail,
These examples are not intended to limit the invention.

Example/ As shown in FIG. 1(A), the entire surface of a substrate made of a glass plate is coated with a coloring paste film. Next, a positive type photoresist (Az/3soJ (Hoechst)) 3 is coated, and after alignment using a photomask tray having a predetermined pattern, it is exposed and developed from the direction of arrow a to form a light-shielding area. The resist l-'Y of the corresponding portion t was removed.The base film for coloring was made of gelatin made photosensitized with ammonium dichromate.

Subsequently, the 7 base films for coloring the photoresist openings were treated for 1 minute in a 1% by weight aqueous solution of the dye shown in Table 1 A at pHs ~ 6 and temperature θ'' ~ 60°C for 1 minute to form a 3M photoregion. Then, the remaining photoresist pattern 3A is removed using a trichlene bath (FIG. 1B).

Subsequently, the entire surface is irradiated with infrared rays f in the direction of the arrow to heat and harden the coloring base film. At this point, since the coloring base film 7 corresponding to the mask pattern S has already been colored black, it absorbs more heat than the coloring base film g in the undyed area. It is baked to a very high density and becomes highly polymerized gelatin.

(Figure 1C).

After that, the front surface was thoroughly washed with water to remove the photosensitizing substance of ammonium dichromate in the coloring base film, and Photoresis 1-, 7B was applied again, and exposed and developed using a photomask with a predetermined pattern. The first colored portion gR is opened and colored with red dye (FIG. 1D).

Next, photoresist 3B is removed and photoresist 3B is removed again.
Coat C, open the other part gG that you want to color, and color it green (11th 3rd).

Below, repeat the same coloring process (repeat to other parts gCY
was colored cyan, and finally a top coat layer 9 made of transparent resin was formed on the surface to complete a color filter (FIG. 1F).

EXAMPLE Co. In place of the dye of the first dye 4/ in Example 1, the λth surface waste S was used.
A light-shielding region was formed in the same manner as in Example 1, except that the dye was used, and a color filter could be manufactured.

Example J A color filter was manufactured by forming a light-shielding region in the same manner as in Example/, except that the dye in Table 3, 7162, was used instead of the dye in Table 1, 46/ in Example/.

EXAMPLE Tei Gelatin photosensitized with ammonium dichromate was coated on a glass substrate and cured by exposure to form a thin film. A coloring test was conducted using the dyes listed in Tables v1/-3 under the dyeing conditions of Example 1, and all were successfully colored.

[Brief explanation of the drawing]

FIGS. 1(A) to 1(F) are process cross-sectional views for explaining a method of fabricating a color filter according to an embodiment of the present invention. /...Substrate, λ, 7, g...Base film for coloring, J...Photoresist, gR%zaG, gOY...Coloring part.

Claims (1)

[Claims] (1) In a color filter having one or more colored layers, at least one of the colored layers has the following general formula [I
] Or, a color filter characterized by containing at least one kind of azo dye represented by [II]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, X is a hydrogen atom, a lower alkyl group, or SO_3M
represents a phenyl group which may be substituted with a group, m and n represent 0 or 1, M is a hydrogen atom, an alkali metal,
It represents ammonium or amines, and A, B and C represent a benzene ring or a naphthalene ring which may have a substituent. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (In the formula, A and B represent a benzene ring or naphthalene ring which may have a substituent, m represents 0 or 1, M
represents a hydrogen atom, an alkali metal, ammonium or amines) (2) The azo dye represented by the above general formula [I] is represented by the following general formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[ III] (wherein Y and Z represent a hydrogen atom, an alkyl group, an alkoxy group, or an acylamino group, and M, C, X, and m have the same meanings as defined above) The color filter according to item 1. (3) The azo dye represented by the above general formula [I] has the following general formula [IV] ▲ There are numerical formulas, chemical formulas, tables, etc.▼・・・・・・[IV] (A, M, X and m have the same meaning as defined above.) The color filter according to claim 1, wherein (4) The azo dye represented by the above general formula [I] has the following general formula [V] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ ... [V] (In the formula, l represents 1 or 2, 2. The color filter according to claim 1, wherein M, Y, X, m, and Z have the same meanings as defined above. (5) The azo dye represented by the above general formula [II] has the following general formula [VI] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ ... [VI] (In the formula, M, l, and B are The color filter according to claim 1, characterized in that it has the same meaning as the definition.