JP3067330B2 - 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 method of manufacturing a color filter for use in a color display such as a liquid crystal display, and more particularly, to a method of manufacturing a color filter by patterning by an exposure method using an oxygen barrier film. On how to do it.

[0002]

2. Description of the Related Art Conventionally, in a method of manufacturing a pigment dispersion type color filter by a pattern exposure method using ultraviolet light, a photosensitive color coloring material is coated on a predetermined color filter substrate, dried, and then exposed to ultraviolet light. Of the pattern reproducibility due to the influence of oxygen at the time of exposure (active ozonation of oxygen in the air by ultraviolet rays used for exposure) (reduction of the ultraviolet crosslinking curing reaction of the photosensitive color filter coloring material) and accelerate the curing reaction To this end, an oxygen barrier film such as polyvinyl alcohol is coated on the surface of the color coloring material, and thereafter, a desired pattern exposure and development treatment are performed to obtain a color filter.

[0003]

In the coating of the oxygen barrier film before the pattern exposure in the above conventional manufacturing method, if the wettability of the oxygen barrier film with respect to the previously coated color coloring material surface is not good, Due to uneven coating film thickness, coating fluid popping or shrinkage due to difference in surface tension, or coating defects such as pinholes, perfect oxygen barrier performance for color coloring materials cannot be obtained. The yield in mass production of color filters was not good.

SUMMARY OF THE INVENTION It is an object of the present invention to uniformly coat an oxygen-blocking film on a photocurable color coloring material so that the adverse effect of oxygen during exposure can be satisfactorily blocked and the production can be performed with good yield. Is what you do.

[0005]

According to the present invention, a color filter is obtained by pattern exposure using a photocurable color filter coloring material in which an alkyl monomer is added to an alkyl polymer resin and a filter coloring pigment is dispersed. In the method for producing a filter, a color filter layer 2 is formed by coating a color filter colorant on a surface of a color filter substrate 1, and a photocurable resin liquid containing a surfactant is added to the color layer. A method of manufacturing a color filter, comprising coating the substrate 1 with an oxygen barrier film 3 and then pattern-exposing the substrate 1 with ultraviolet light in a predetermined color filter pattern.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention will be described in detail with reference to the embodiments shown in FIGS. 1 (a) to 1 (c). (A) An alkyl polymer resin and an alkyl monomer Resin, filter coloring pigment (Blue corresponding to the three primary colors of light, Green, respectively)
(Green or red), a photo-curable (ultraviolet cross-linkable) color filter coloring material obtained by kneading a pigment-based dispersant, a polymerization initiator, and an organic solvent. After the layer 2 is coated and dried, a translucent (transparent to translucent) photocurable polyvinyl alcohol to which a surfactant is added is coated on the colorant layer 2 and then dried to form an oxygen barrier film. Form 3

Subsequently, (b) the transparent portion and the opaque portion are formed from the upper side of the color filter substrate 1 in which the colorant layer 2 and the oxygen blocking film 3 to which the surfactant is added are laminated in this order in a dry state. Pattern exposure of ultraviolet light L through a photographic master having a desired filter pattern consisting of, or pattern exposure of ultraviolet light L using ultraviolet scanning exposure means, and photocuring by photocrosslinking and curing the irradiated portion of the ultraviolet light L The uncured portion 5 is formed in a portion where the portion 4 is not irradiated with the ultraviolet light L by patterning the portion 4.

Subsequently, (c) the uncured portion 5 is dissolved and removed with a predetermined solvent, and
This is to obtain a desired color filter pattern 6 including the photo-cured portion 4.

The steps shown in FIGS. 1 (a) to 1 (c) are respectively performed by using blue (green) pigment, green (green) pigment, and red (red) pigment to obtain blue, green, and red photosensitive colors. For each of the filter coloring material layers, the irradiation position of the ultraviolet light L for pattern exposure is, for example, Blue (hereinafter referred to as B) or Gre if the color filter pattern is a stripe pattern.
en (hereinafter referred to as "G") and Red (hereinafter referred to as "R") are exposed by pattern exposure while being moved by 1/3 width with respect to the full width of each of the three colors. The color filters arranged next to each other are obtained.

The alkyl polymer resin used in the method of the present invention includes acrylic resin, polyethylene resin, polyvinyl chloride resin, polystyrene resin, polypropylene resin, polyvinyl acetate resin, or a blend resin mainly composed of any of these. Copolymer resins can be used.

The color filter coloring pigment (dye) used in the present invention is preferably heat-resistant and weather-resistant. For example, barium sulfate, zinc white, lead sulfate, titanium oxide, yellow lead, red iron oxide, ultramarine blue , Navy blue, chromium oxide, inorganic pigments such as carbon black, benzene yellow,
Benzin Yellow, Resol First Orange, Vulcan First Orange, Pigment Scarlet,
Any one of organic pigments such as thioindigo, green gold, malachite green lake, liotogen red, lionogen orange, lionol green, lionogen yellow, lionol blue, and lionogen violet is mixed at an appropriate ratio to obtain light emission. A color pigment corresponding to the three primary colors, that is, a B-color pigment having a high spectral transmittance in a wavelength range of 400 nm to 500 nm;
a G color tone pigment having a high spectral transmittance in a wavelength range of
and a pigment having an R color tone having a high spectral transmittance in a wavelength range of 700 nm to 700 nm.

As the dispersant used in the present invention, derivatives of organic dyes can be used, and azo-based, phthalocyanine-based,
Quinacridone-based, anthraquinone-based, perylene-based, perinone-based, thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, triphenylmethane-based, organic complex dyes such as metal complex salts such as copper complex salts and the like, a hydroxyl group, A derivative having a substituent such as a carboxyl group, a sulfonic acid group, a carboxylic acid amide group, or a sulfonic acid amide group can be used.

Examples of the polymerization initiator used in the present invention include acetophenone, benzophenone, benzyldimethyl ketal, benzoyl peroxide, 2-chlorothioxanthone and the like (manufactured by Daito Chemical Industry Co., Ltd .; , Ciba-Geigy, Osaka Organic Synthetic Chemical Industry Co., Ltd.).

As the alkyl-based monomer resin used in the present invention, a monomer type of the resin used as the alkyl-based polymer resin is used, and a bifunctional monomer or a trifunctional monomer can be used. For example, when an acrylic polymer resin is used as the alkyl-based polymer resin, as the bifunctional monomer,
1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol, diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) phenol A, 3-
Methylpentanediol diacrylate and trifunctional monomers include trimethylolpropane triacrylate, pentaerythritol triacrylate, and tris (2-hydroxyethyl) isocyanate (Showa Polymer Co., Ltd., Toa Gosei Chemical Industry Co., Ltd.), and the like. Can be used.
In the case of an ethylene polymer resin, an ethylene monomer is used, and in the case of a styrene polymer resin, a styrene monomer resin is used.

As the solvent mixed as a solvent in the color filter coloring material used in the present invention and the solvent used as a developer, an organic solvent can be used.
Methyl cellosolve, ethyl cellosolve, cyclohexane, xylene, etc., or a mixed solvent thereof can be used.

The coloring pattern of the color filter may be a square (rectangular) block pattern such as a checkered pattern in addition to the above-mentioned stripe pattern. Hereinafter, a specific example of the method of the present invention will be described with reference to FIG.
(C) and FIGS. 2 (a) to (e).

<Example 1> Of the photocurable color filter colorants of B, G, and R each comprising a polymerized acrylic resin, a color pigment, a dispersant, an acrylic resin monomer, a polymerization initiator, and a solvent. , B colorant, FIG.
(A) Spin coating (rotational coating) method, dipping (pulling) on glass substrate 1 so as to have a film thickness of 20 μm
A color filter coloring material layer 2 having a Bu color tone is formed on the substrate 1 by coating using a coating method, a roll coating method, or the like.

Subsequently, 1 k of commercially available polyvinyl alcohol
g (concentration 5%) with a silicon-based surfactant (KF351)
A, manufactured by Shin-Etsu Silicone Co., Ltd.), and using a photo-curable resin liquid for forming a transparent oxygen barrier film obtained by stirring for 10 minutes, the color of the substrate 1 was changed as shown in FIG. On the filter coloring material layer 2, coating is performed by the same coating method as described above so that the film thickness becomes 1 μm, and dried.
An oxygen barrier film 3 is formed.

Subsequently, from the side of the B color tone material layer of the substrate,
Transparent line width: An opaque line width is subjected to a stripe pattern exposure of ultraviolet light L through a photographic master having a fine stripe pattern of 1: 2, or a stripe pattern exposure of ultraviolet light L by a scanning exposure (spot exposure) method. Ratio 1/3
The light-cured portion 4 is obtained by photo-curing the B colorant layer (and the oxygen blocking film 3 thereon) at the transparent line width portion. (FIG. 1 (b)
reference)

Subsequently, development is carried out using an organic solvent such as xylene, and the uncured portion 5 not irradiated with ultraviolet rays is dissolved and removed. As shown in FIG. 1 (c), the three primary colors B, This is to obtain a stripe pattern 6 for a single color filter of B color tone having a width 1/3 of the total width of the three stripe patterns G and R.

Next, as shown in FIG. 2 (a), a G (green) color filter coloring material is formed on the substrate 1 on which the above-mentioned Bu color stripe pattern 6 is formed so as to have a thickness of 20 μm. After coating by a coating method and drying to form a colorant layer 12 having a Bu color tone, a surfactant is added to the upper side of the colorant layer 12 having a Bu color tone to form a transparent oxygen barrier film similar to the above-described one. A photocurable resin liquid is coated to a thickness of 1 μm and dried to form an oxygen barrier film 13.

Subsequently, as shown in FIG. 2B, a photographic master having a fine stripe pattern having a transparent line width: opaque line width of 1: 2 as described above (see FIG. 1B) is used. The ultraviolet light L is exposed to a stripe pattern at a position adjacent to the stripe pattern 6, or the ultraviolet light L is applied to the stripe pattern 6 by a scanning exposure (spot exposure) method.
Exposure to a stripe pattern at a position adjacent to
The G coloring material layer 12 (and the oxygen blocking film 13 thereon) at the transparent line width portion of / 3 is light-cured to obtain a light-cured portion 14.

Subsequently, similarly to the above (see FIG. 1C), the uncured G (green) colorant layer 12 on the substrate 1 which has not been exposed to ultraviolet light is developed with an organic solvent such as xylene. The uncured G-tone coloring material layer 12 and the oxygen blocking film 13 which have not been exposed to ultraviolet light and which are coated on the previously formed stripe pattern 6 and the oxygen blocking film 13 and the oxygen blocking film 13 are then coated with an organic solvent developer ( FIG. 2 (c)
As shown in FIG. 2, a stripe pattern 7 of G (green) color is formed adjacent to the stripe pattern 6 of B (blue) color to obtain stripe patterns 6 and 7 for two-color (B, G) color filter. Things.

Next, FIG. 2D, B (blue), G
On the substrate 1 on which the (green) two-color color filter stripe patterns 6 and 7 are formed, a color filter coloring material of R (red) tone is coated by the same coating method as described above so as to have a film thickness of 20 μm. After drying to form the R color tone colorant layer 22, a photocurable resin for forming a transparent oxygen barrier film similar to the above, to which a surfactant is added, on the upper side of the R tone colorant layer 22 The solution is coated to a thickness of 1 μm and dried to form an oxygen barrier film 23.

Subsequently, an ultraviolet light L is applied to a position adjacent to the stripe pattern 7 in FIG. Is exposed to a stripe pattern or a position adjacent to the stripe pattern 7 is exposed to ultraviolet rays L by a scanning exposure (spot exposure) method, and coated on the upper side of the stripe patterns 6 and 7 by the same method as described above. By developing and removing the uncured colorant layer 22 and the oxygen barrier film 23 which are not irradiated with ultraviolet rays, the stripe pattern 6 adjacent to the B (blue) color tone pattern 6 having the same width as shown in FIG. An R (red) color stripe pattern 8 is formed adjacent to the G (green) color stripe pattern 7.

Thus, a color filter in which stripe patterns 6, 7, and 8 for three-color (B, G, R) color filters are alternately arranged adjacent to each other is obtained. Inspection of the color filter obtained by the above method revealed no pinholes in the color stripe pattern and non-uniform coloring density due to a delay in the photocuring crosslinking reaction due to poor coating of the oxygen barrier film.

Example 2 B (blue), G (green), R (red) comprising a polymerized acrylic resin, a pigment, a dispersant, an acrylic resin monomer, a polymerization initiator, and a solvent
Of the photocurable color filter coloring materials of the respective colors described above, a B (blue) coloring material is applied onto the glass substrate 1 by a spin coating (rotational coating) method so as to have a film thickness of 20 μm. Then, coating is performed by a dipping (pulling up) method, a roll coating method, or the like, and dried to form a color filter coloring material layer 2 having a Bu color tone on the substrate.

Then, commercially available polyvinyl alcohol 1k
g (concentration 5%) with a fluorine-based surfactant (FC-170).
C, manufactured by Sumitomo 3M Co., Ltd.), and using a photocurable resin liquid for forming a transparent oxygen barrier film obtained by stirring for 10 minutes, a color filter coloring material layer 2 of the substrate was prepared.
On top of this, the coating film is coated by the same coating method as described above so as to have a film thickness of 1 μm, dried, and
To form (See Fig. 1 (a))

Next, in FIG. 1B, ultraviolet rays L are striped from the Bu colorant layer side of the substrate through a photographic master having a fine stripe pattern having a transparent line width: opaque line width of 1: 2. Pattern exposure, or stripe exposure of ultraviolet rays by scanning exposure (spot exposure) method, photo-curing the coloring material of the transparent line width portion of the ratio 1/3,
A light-cured part 4 is obtained.

Subsequently, development was performed using an organic solvent such as xylene, and each of the B
By dissolving and removing the uncured portions 5 of the u-tone coloring material layer 2 and the oxygen blocking film 3 with a developing solution, the total width of the three stripe patterns of the three primary colors B, G, and R required for the color filter is reduced. Thus, a stripe pattern 6 for a single color filter of B (blue) tone having a 1/3 width is obtained.

Thereafter, Example 1 as shown in FIGS. 2A to 2E was used except that the above-mentioned fluorine-containing surfactant was used as the coating liquid for forming the oxygen barrier film.
G (green) color stripe pattern 7, R
By exposing and aligning the (red) color stripe pattern 8, a color filter in which blue, green, and red three-color stripe patterns 6, 7, and 8 are alternately and sequentially arranged is obtained.

Examination of the color filter obtained by the above method revealed no pinholes in the color stripe pattern and non-uniform coloring density due to a delay in the photocuring crosslinking reaction due to poor coating of the oxygen barrier film.

[0033]

According to the method of the present invention, a colorant for a photocurable color filter is applied to a substrate for a color filter such as a glass plate, a synthetic resin plate, a synthetic resin film and dried, and then a surfactant is applied to the surface of the colorant. Since the oxygen-blocking film is formed by coating the added light-transmitting photocurable resin liquid for forming the oxygen-blocking film, the surfactant is used to improve the wettability of the oxygen-blocking film on the surface of the colorant for the color filter. It is possible to prevent the nonuniformity of the coating thickness of the oxygen barrier film and the occurrence of pin poles as in the related art.

Accordingly, the oxygen blocking performance of the color filter coloring material is increased, and the speed and performance of the photocrosslinking curing reaction of the photosensitive color filter coloring material due to the influence of oxygen can be prevented from lowering and nonuniformity can be prevented. It can prevent uneven color density of the color filter pattern and generation of pinholes due to uneven curing reaction of the colorant.

[0035]

The method of the present invention uses a photocurable color filter coloring material such as B (blue), G (green) and R (red) to form a block pattern such as a stripe pattern or a checkered pattern. Form a color filter pattern by pattern exposure, in the method of manufacturing a color filter, by applying a photo-curable resin liquid with a surfactant added to the surface of the color filter coloring material before UV exposure, uniform It is characterized by forming an oxygen barrier film, which can more accurately block the contact between the surface of the color filter coloring material and oxygen in the air at the time of ultraviolet irradiation, and can be more accurately blocked than before. Ozone generated from oxygen in the air does not slow down the progress of the UV curing reaction, and avoids uneven curing reaction, Such there is a color filter can be produced the effect of quality.

[Brief description of the drawings]

FIG. 1 is a side view of an embodiment illustrating a step of forming a oxygen blocking film and obtaining a colored pattern of a single color filter in the method of the present invention.

FIG. 2 is a side view of an example illustrating a step of forming an oxygen blocking film and obtaining a colored pattern of a three-color filter in the method of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate for color filters 2 ... Blue coloring material layer 3
... Oxygen blocking film 4 ... Light cured part 5 ... Uncured part 6,7,
8 ... Color filter stripe pattern 12 ... Green coloring material layer 13 ... Oxygen blocking film 14 ... Light cured part 2
2 ... Red coloring material layer 23 ... Oxygen blocking film L ... Ultraviolet light for pattern exposure

Claims (3)

(57) [Claims] The present invention relates to a method for producing a color filter by pattern exposure using a photocurable color filter coloring material in which an alkyl monomer is added to an alkyl polymer resin and a filter coloring pigment is dispersed. The surface of the substrate 1 is coated with a photocurable color filter coloring material to provide a coloring material layer 2, and a photocurable resin solution containing a surfactant is coated on the coloring material layer to form an oxygen barrier film 3. After the formation, a method of manufacturing a color filter, comprising subjecting the substrate 1 to pattern exposure to ultraviolet light in a predetermined color filter pattern. 2. The method for producing a color filter according to claim 1, wherein the photocurable resin liquid is polyvinyl alcohol. 3. The method for producing a color filter according to claim 1, wherein the surfactant is a silicon-based or fluorine-based surfactant, or a surfactant using a combination of a silicon-based and a fluorine-based surfactant. .