JPH0823606B2 - Color filter - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color filter. Specifically, it relates to a color filter mounted on a color TV.

[Conventional technology]

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

First, as the first manufacturing method, on a glass substrate that has been subjected to optical polishing, a sensitizing liquid such as polyvinyl alcohol, glue, gelatin, and casein, which has been made photosensitive with ammonium dichromate, is roller-coated and dipping. After applying evenly with a spinner etc. and drying, photo-curing only the pattern part of the first color with a mask exposure method, developing and removing other than the required pattern to form a dyed base film, and then the prescribed spectral characteristics. The base film is dyed with a dye having ## STR3 ## to dye the first color pattern. Next, a transparent dye-proof film which is not dyed with a dye is applied to the entire surface.

Next, in the same manner, uniformly apply the same photosensitive solution as above,
After drying, it is exposed and developed by a mask exposure method to form a dyed base film for the second color and then dyed with a second dye having a predetermined spectral characteristic. Further, the transparent dye-proof film is applied to the entire surface.

Next, in the same manner, uniformly apply the same photosensitive solution as above,
After drying, it is exposed and developed by a mask exposure method to form a dyed base film for the third color, and dyed with a third dye having a predetermined spectral characteristic.

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

However, in such a color filter method, the substrate conditions are different when forming the first-color dyeing base film, the second-color dyeing base film, and the third-color dyeing base film. That is, the first color dyeing base film is directly formed on the glass substrate, while the second color dyeing base film is formed on the first color dye-proof film, and the third color dyeing base film is It is formed on the second color resist film.

On the other hand, the adhesion of the photosensitive liquid differs between the glass substrate and the respective stainproof films. Therefore, when a photosensitive liquid having good adhesion is used for the glass substrate, peeling easily occurs at the interface of the dye-proof film, and in such a conventional color filter manufacturing method, a lot of peeling defects occur. Furthermore, since each of the dye-proof coatings is present,
There are steps on the dyed base films for the first, second and third colors,
The resolution of the pattern becomes lower as the second and third colors are formed. That is, there was a defect that the patterns of the dyed base films of the second and third colors were blurred.

On the other hand, as a second manufacturing method, a light shielding pattern, for example, a metal layer made of a vapor deposition film of Cr (chrome) or the like is formed in a stripe shape on a light transmissive glass substrate. Here, the metal film is used as a light-shielding film in order to prevent optical noise from entering other than the photodiode portion of the solid-state image sensor.

Next, a dyeing base film (hereinafter referred to as a resin film) is formed on the glass substrate to a thickness of 3 to 5 μm.

Next, a commercially available photoresist is coated on the resin film to a thickness of about 5000Å using a dye-proof film such as a spinner, and dried at 60 to 75 ° C for 5 to 10 minutes.

Then, a glass plate having a mask of a predetermined pattern formed of emulsion or Cr is placed on the photoresist and irradiated with light from a mercury lamp.

Next, the exposed photoresist is developed. As a result of the development, the exposed portion is dissolved away, and the unexposed portion, that is, the dye-proof film mask and the dissolved portion, that is, the unmasked portion are selectively formed. This dye-proof film mask must prevent the dye from penetrating in the next step.

Next, the resin film selectively covered with the dye-proof film mask is dipped in a dye such as Congo red for 30 to 40 seconds, and colored red through the non-masked portion. Then, a red colored region is formed on the resin film.

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

Then, a glass plate provided with a mask having a pattern different from the above-mentioned mask is placed on the photoresist, and light is irradiated with a mercury lamp.

The exposed photoresist is then developed to dissolve away the exposed areas and leave the unexposed areas. That is, a dye-proof film mask and an unmasked portion are formed.

Next, the resin film selectively covered with a dye-proof film mask is mixed with a dye such as Suminol Yellow and Patent Blue 30
Soak for ~ 40 seconds and stain green through the unmasked area.
Then, a green colored region is formed adjacent to the red colored region.

Then, a dye-proof film mask and an unmasked portion are formed in the same manner as described above.

Then, the resin film selectively covered with the dye-proof film mask is dipped in a dye such as diamond cotton blue to form a blue colored region. Then, the dye-proof film mask is removed to obtain a color filter, that is, a color filter having a red colored region, a green colored region, and a blue colored region.

However, this second manufacturing method cannot completely prevent the dye from spreading in the lateral direction during dyeing, and the width of the metal layer formed at the boundary is 2-3 μm and the dyeing base film thickness is 1 μm or more. In that case, there is a drawback that the color mixture with the adjacent color will no longer occur and the optical characteristics of the filter will deteriorate.

In order to improve the drawbacks of these conventional methods, JP-A-59-50411
Is proposed.

That is, the color separation area is colored black in advance to form a light-shielding area, and then the entire surface is irradiated with heat rays to harden the black-colored base film having good absorption of heat rays to solidify the high polymerization color separation area. However, there has been proposed a method for manufacturing a color filter, which is characterized in that a colorant is prevented from laterally diffusing beyond the color separation region in a coloring step which is a subsequent step.

[Problems to be solved by the invention]

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

[Means for solving problems]

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

(2) It has sufficient absorption at 390 to 700 nm in terms of spectral characteristics.

(3) It has excellent fastness such as light resistance and heat resistance.

It was found that the dyes represented by the following general formulas [I] and [II] are excellent in meeting these requirements, and the present invention has been accomplished.

That is, the present invention is to provide a color filter containing a black dye, an object of which is to provide a color filter having one or a plurality of colored layers, at least one of the colored layers having the following general formula [I] or [II]. ] It is achieved by the color filter characterized by containing at least 1 sort (s) of the azo dye shown by these.

(In the formula, X represents a hydrogen atom, a lower alkyl group or a phenyl group which may be substituted with a SO ₃ M group, and m is 0 or 1
Represents a hydrogen atom, an alkali metal, ammonium or an amine, and A, B and C represent a benzene ring or a naphthalene ring which may have a substituent.

(In the formula, A and B represent a benzene ring or a naphthalene ring which may have a substituent, m represents 0 or 1, and M represents
Represents a hydrogen atom, an alkali metal, ammonium or amines) Hereinafter, the present invention will be described in detail.

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

(In the formula, X represents a hydrogen atom, a lower alkyl group or a phenyl group which may be substituted with a SO ₃ M group, and m is 0 or 1
Represents a hydrogen atom, an alkali metal, ammonium or an amine, and A, B and C represent a benzene ring or a naphthalene ring which may have a substituent. ) (In the formula, A and B represent a benzene ring or a naphthalene ring which may have a substituent, m represents 0 or 1, and M represents
Represents a hydrogen atom, an alkali metal, ammonium or amines. Further, as the dye of the general formula [I], it is preferable to use the dye represented by the following general formula [III], and the dye of the general formula [II] The dye is preferably represented by the following general formula [VI].

(In the formula, Y and Z represent a hydrogen atom, an alkyl group, an alkoxy group, and an acylamino group, and M, C, X, and m have the same meanings as defined above.) (In the formula, M, l, and B have the same meanings as defined above.) Specific examples of the dyes used in the invention include those shown in Tables 1 to 3.

The dyes of the present invention include, for example, ordinary diazotization and coupling according to the description of “New Dye Chemistry” by Yutaka Hosoda (published on December 21, 1973) Gihodo, page 397, line 27 to page 398, line 19. It can be manufactured by repeating.

The color separation area can be colored black with the dye of the present invention based on the following method.

That is, the light-shielding region forming portion is provided with a dye of the present invention 0.1 to 10.0%, preferably 0.5 to 2% aqueous solution, pH 3 to 8, preferably 4 to
5, at a temperature of 30 to 100 ° C., preferably 50 to 70 ° C., the mixture is treated for 5 to 20 minutes in a dyeing bath adjusted by adding salt or the like if necessary, to thereby make it a light-shielding region.

It is possible to sufficiently shield light in the range of 390 to 700 nm by using the dye of the present invention, but it is also effective to supplementarily use the following dyes for completeness.

CIDirect Yellow-86 CIDirect Yellow-142 CIAcid Yellow-25 CIAcid Orange-28 CIAcid Orange-43 CIAcid Orange-19 CIAcid Green-25 [Examples] The present invention will be described in more detail with reference to Examples below. It does not limit the invention.

Example 1 As shown in FIG. 1 (A), a substrate 1 made of a glass plate is coated in advance with a base film 2 for coloring the entire surface.
Next, positive photoresist [AZ1350J (Hoechst)]
Photomask 4 coated with 3 and having a predetermined pattern
After alignment by using, the resist is exposed in the direction of arrow a and developed to remove the resist in the portion 6 corresponding to the light-shielding region forming portion. The coloring base film 2 was made of gelatin, which was made photosensitive with ammonium dichromate.

Subsequently, the coloring base film 7 in the photoresist opening is formed.
Table 1 No. 1 dye 1% by weight aqueous solution pH 5 ~ 6, temperature 50
Treated for 15 minutes at 60 ° C to 60 ° C to form a light-shielded area, and the photoresist pattern left by the solvent of trichlene
Remove 3A (Fig. 1B).

Then, the entire surface is irradiated with infrared rays in the direction of arrow b to harden the coloring base film. At this time, since the coloring base film 7 corresponding to the space between the mask patterns 5 is already colored black, it absorbs heat rays better than the uncolored portion of the coloring base film 8 and is extremely strong. It is hardened by high density and becomes highly polymerized gelatin. (FIG. 1C).

After that, the front surface is thoroughly washed with water to remove the photosensitizing substance of ammonium dichromate in the coloring base film, the photoresist 3B is applied again, and the photoresist 3B is exposed and developed using a photomask having a predetermined pattern. Open the colored part 8R,
It is colored with a red dye (Fig. 1D).

Next, the photoresist 3B is removed, and the photoresist 3C is removed again.
Is coated, the other portion 8G desired to be colored is opened, and it is colored green (FIG. 1E).

Hereafter, repeat the same coloring process and other parts 8CY
Was colored in cyan, and finally a top coat layer 9 made of a transparent resin was formed on the surface to complete a color filter (FIG. 1F).

Example 2 Instead of the dye of No. 1 in Table 1 in Example 1, N in Table 2 was used.
A light-shielding region was formed in the same manner as in Example 1 except that the dye of o.5 was used, and a color filter could be manufactured.

Example 3 Instead of the dye of Table 1 No. 1 in Example 1, Table 3 N
A light-shielding region was formed in the same manner as in Example 1 except that the dye of o.2 was used, and a color filter could be manufactured.

Example 4 Gelatin sensitized with ammonium dichromate was coated on a glass substrate and exposed to light to cure to form a thin film. Coloring tests were carried out on the dyes of Tables 1 to 3 under the dyeing conditions of Example 1, and good coloring was obtained in all cases.

[Brief description of drawings]

1A to 1F are process cross-sectional views for explaining a method of manufacturing a color filter according to an embodiment of the present invention. 1 ... Substrate, 2, 7, 8 ... Base film for coloring, 3 ... Photoresist, 8R, 8G, 8CY ... Coloring part.

Claims (3)

[Claims] 1. A color filter having one or more colored layers, wherein at least one of the colored layers contains at least one azo dye represented by the following general formula [I] or [II]. Characteristic color filter. (In the formula, X represents a hydrogen atom, a lower alkyl group or a phenyl group which may be substituted with a SO ₃ M group, and m is 0 or 1
Represents a hydrogen atom, an alkali metal, ammonium or an amine, and A, B and C represent a benzene ring or a naphthalene ring which may have a substituent. ) (In the formula, A and B represent a benzene ring or a naphthalene ring which may have a substituent, m represents 0 or 1, and M represents
Represents a hydrogen atom, alkali metal, ammonium or amines) 2. The color filter according to claim 1, wherein the azo dye represented by the general formula [I] is represented by the following general formula [III]. (In the formula, Y and Z represent a hydrogen atom, an alkyl group, an alkoxy group, and an acylamino group, and M, C, X, and m have the same meanings as defined above.) 3. The color filter according to claim 1, wherein the azo dye represented by the general formula [I] is represented by the following general formula [IV]. (In the formula, M, l, and B have the same meanings as defined above.)