JPH0336502A - Color filter - Google Patents

Abstract

PURPOSE:To obtain the color filter imposed with a blue colored film having a color characteristic, light resistance and heat resistance in combination by using specific water soluble anthraquinone compds. or a mixture composed thereof as a blue dye for the color filter. CONSTITUTION:The color filter formed by imposing the film colored in the form of patterns to plural hues on a base body is so formed that at least one of the patterns is colored by the water soluble anthraquinone compds. expressed by formula I or the mixture composed thereof. While this method is particularly useful if the base material to be colored is a photosetting synthetic resin of an acrylic system, the material is not limited thereto and this method is applicable even to the case of natural base materials. Further, the elution of the dye from a fixing bath to the colored layer which is of a problem at the time of the production entailing the fixing reserve printing treatment of the production process is obviated and the fixing reserve printing capacity is excellent. The color filter imposed with the blue colored film having the resistance to light and heat and the color characteristic in combination is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to color filters. For more details,
This invention relates to color filters with excellent optical properties used in liquid crystal display devices, color separation devices, sensors, etc.

The conventional dyeing method for manufacturing color filters involves forming a transparent thin film-like film of synthetic resin containing cationic/sexual groups in the form of stripes or mosaics (called a pattern) on the surface of a substrate such as glass or silicon wafer. Alternatively, a coat of protein-based natural polymer substances such as gelatin, casein, or glue is provided as a colored film, and this is dyed (colored) using a dye.
The basic principle is to do so. The following three methods are known as specific manufacturing processes for color filters.

(1) After a film to be colored is provided on the surface of the substrate, it is exposed to light through a mask and developed, and the resulting pattern is dyed to form a colored layer. Next, a non-colored protective coating film is provided over the entire surface, and a second colored film is provided thereon by the same procedure as described above. Thereafter, colored layers are sequentially laminated as necessary.

(2) After forming a film to be colored on the surface of the substrate, it is exposed to light through a mask, developed, and the resulting pattern is dyed to form a colored layer. After that, the dye is fixed and resisted with tannic acid, etc. Apply. A second coating to be colored is provided by a similar operation. Thereafter, if necessary, a colored layer is formed on the same substrate surface.

((8) A film to be colored (colored film) is provided on the surface of the substrate. After a positive resist layer is provided on it, it is exposed to light through a mask and developed, and the colored film exposed in a pattern is dyed. Then, the positive resist layer is peeled off to form a colored part.The operations after forming the positive resist layer are repeated to dye the same colored film in a plurality of colors in a desired pattern.

Color filters manufactured using the above process usually have three primary colors, R (red),
G (green), B (blue), or Y (yellow), which is the three complementary primary colors
, M (magenta), C (cyano), (M may be omitted). The most important property required of a color filter is its optical property, and the spectral properties of each colored layer largely control both values of the final product.

It also has a high degree of resistance to heat treatments encountered in the manufacturing process of liquid crystal display devices equipped with color filters, such as the sputtering process for forming transparent electrode layers, and to light applied during use as a final product. have,
The predetermined optical properties must not be impaired. Naturally, the dyes applied must also have good solubility and solubility in water and be stable for long periods in acidic dye baths.

Furthermore, when a process that requires fixing treatment is involved, it is required that the fixing treatment effect be excellent. By the way, since protein-based natural polymer substances such as gelatin, caseino, and glue have cationic groups, they can be dyed (colored) with water-soluble anionic dyes. In addition, when using a photocurable synthetic resin base material instead of these, by retaining cationic groups in the resin component, it can be dyed with water-soluble anionic dyes in the same way as protein-based natural polymer substances. Become so.

SUMMARY OF THE INVENTION A number of water-soluble anionic dyes have been investigated, either alone or in combination, to obtain desired optical properties. However, for the primary color blue, especially when using a photocurable synthetic resin with cationic groups as the substrate to be colored, it must have the desired color characteristics and sufficient resistance to heat and light, and It is particularly difficult to select a dye with excellent fixing performance, and at present no satisfactory dye has been found.

The spectral properties required for the desired blue dye are 5QQn
The wavelength that gives 50% transmittance of the colored film dyed so that the transmittance in the vicinity of m is 1% or less (T = 50
%) is at 490±lQnm, and from 440 to 4600m
This means that the transmittance in the region is as high as possible. In order to satisfy such optical characteristics, triphenylmethane dyes such as Color Index Acid Blue 83 and Color Index Acid Blue 90 are conventionally used. The spectral transmittance curves of these dyes are sharp and the colors are clear, and when the substrate to be colored is a natural protein such as gelatin, casein, or gris, or a polyimide-based synthetic resin, the color characteristics of the colored film and the light and Although its resistance to heat is insufficient, it is not impossible to use it. On the other hand, when the base material to be colored is a synthetic resin having a photocurable cationic group, especially when the main chain polymer is an oil made of acrylic acid and its derivatives, the resistance to heat and light is extremely poor and it cannot be put to practical use. I don't get it.

Anthraquinone/structure is known as a blue dye with relatively hard heat resistance and/or light resistance, but there are few dyes that meet the required optical properties, and even those that meet the optical properties are limited to the aforementioned photocurable acrylic dyes. When applied to synthetic resins, heat resistance and/or light resistance are significantly inferior. For example, when a colored film using an anthraquinone compound of the following formula is exposed to light, the color changes significantly to red in a short period of time, making it impossible to put it to practical use.

Therefore, it is desired to develop a color filter equipped with a blue colored film that has both light and heat resistance and color properties.

Means for Solving the Problems The inventors of the present invention made earnest efforts to find a color filter that has both the optical properties and durability as described above, and as a result, a color filter dyed (colored) with a specific anosthraquinone compound was developed as described above. The present invention was discovered based on the discovery that it has such color characteristics and excellent reliability (resistance to heat and light). That is, the present invention provides a color filter in which a film colored in a plurality of hues in a pattern is placed on a substrate, in which at least one pattern 7 has the following formula (1).
Provided is a color filter colored with a water-soluble anthraquinone compound or a mixture thereof. In particular, in the present invention, the substrate to be colored is
It is particularly useful in the case of lyle-based photocurable synthetic resins, but
It goes without saying that the method is not limited to this, and can also be applied to natural base materials. Furthermore, the manufacturing process mentioned above (
There is no elution of the dye from the colored layer into the fixing bath, which is a problem during production involving the fixing resist dyeing treatment of No. 21, and the fixing resist dyeing ability is excellent.

In C formula (1), X and Y are each independently H or CH
2CH2OO, or M is H, Na, K, Li.

NI(,,NH,CH2CH,OH,NH2(CH2C
H20H), or NH(CH,CH20H)3, respectively. ] The color filter of the present invention will be explained in detail.

The water-soluble anthraquinone compound represented by formula (1) used in the color filter of the present invention is disclosed in JP-A-54-830.
32 et al.

An example of the color filter of the present invention will be explained using the drawings. Figure 1 (aJ to (h)) is a diagram showing a method of manufacturing a color filter using a lamination method in which colored layers of different colors are laminated on a glass plate (substrate). In Figure 1, 1 is a glass plate, 2 is a A thin film of light-curing or colorable resin, etc., provided by spin-coding, 2' is a film to be colored by photo-curing 2 through a mask, 2'' is a colored layer, 3 is a non-staining protective film, and 4 is a film to be colored. 5 is a photomask, 5 is a second colored layer, and 6 is a non-stainable protective film.

A mixture of a protein-based natural polymer such as gelatin, casei 7, or glu and a dichromate such as ammonium dichromate or a photocurable synthetic resin composition having a cationic group is applied onto a glass plate 1 using a spin coach ink. A photocurable thin film 2 having a thickness of 0.2 to 2 μm is provided by coating by a method such as , roller coating, etc. (FIG. 1(b)).

Next, a photomask 4 having a predetermined pattern 7 on the thin film
The exposed portion f is cured by irradiating it with ultraviolet light. (1st
Figure 1 (C)) Next, the unexposed areas are removed by developing with water or the like to form a colored layer 2' with a predetermined pattern. The first colored layer 2' is formed by dyeing with a dye having the following properties (FIG. 1(e)).

Next, a non-staining protective film 3 is applied over the entire surface (Fig. 1(f)).
.

Next, a photocurable coating layer for obtaining a colored layer is provided on the protective film 3 in the same manner as described above, and exposed through a mask and developed to form a colored layer in a predetermined pattern. let me,
In order to obtain a second color, a second colored layer 5 is formed by dyeing with a dye having predetermined optical properties (FIG. 1(g)).
.

Next, a non-staining protective film 6 is provided on the entire surface (first fifth
)). This operation can be repeated to form a colored layer of a third color, or even a colored layer of a fourth color.

In direct-cut color separation color filters for solid-state imaging devices or color sensors, a flattening layer is provided on a silicon wafer that serves as a base, on which a light-detecting section, etc. is provided, and a colored layer is applied on top of the silicon wafer using the same procedure as described above. can be formed,
The same material as the non-staining protective film can be used for the planarization layer.

In the present invention, it is essential to use a water-soluble anthraquinone compound represented by the formula (1) or a mixture thereof as a dye to obtain a primary color B (blue) colored layer. It is used as a display color filter because the blue colored layer has excellent color properties and has good resistance to the heat applied during the manufacturing process of devices incorporating color filters and good light resistance required for the final product. A color image with well-balanced color can be obtained, and faithful color reproducibility can be obtained as a color separation color filter.

Protein-based natural polymer substances such as gelatin, casein, and glue as the film to be colored in the present invention will be explained. Gelatin is an animal protein that is irreversibly made water-soluble by boiling collagen with water. Gelatin is extracted from animal bones, skin, intestines, etc. by boiling it with water. Casein is a phosphorus protein that is the main component of milk. A dichromate such as ammonium dichromate is added to an aqueous solution of these natural proteins, and the coated layer is cured by applying ultraviolet rays after uniformly coating it on a substrate such as glass using spin coating or roller coating. , a water-insoluble film is formed.

Examples of the synthetic resin having a cationic group as the coloring material used in the present invention include a polymer having a photoreactive unsaturated group and a 4R ammonium base in the side chain, a photopolymerization initiator, and a solvent. A resin composition prepared by dissolving a cationic group-containing polymer in which a photocrosslinking group such as chalcone, cinnamic acid, azide, stilbazole group, or epoxy group has been introduced into the polymer in advance, or in water or an organic solvent; Examples include resin compositions obtained by adding a photocrosslinking agent, such as a diazo compound, azide, or a diazide compound to a polymer obtained by polymerizing a nitrogen-containing monomer as one of the essential constituents, and diluting the mixture with an organic solvent.

The photoreactive resin composition is thus applied to the surface of a substrate and cured by irradiation with actinic light such as ultraviolet rays to obtain a film.

To dye (color) the film using the anthraquinone compound represented by formula (1), for example, a dipping method or a printing method is used, and a dipping method using an aqueous solution is particularly convenient. In this case, it is usually 0.1 to 30g, preferably 1
The base material provided with the above-mentioned film is immersed in a 10-100°C dye bath in which ~1 og of the anthraquinone compound of formula (1) is dissolved in 11 parts of water, usually for 10 seconds or more and about 60 minutes, then taken out, washed with water, and dried. do. The blue-colored film thus obtained exhibits optical properties suitable for use as a color filter.

A method for providing a non-staining protective film is a negative-type 7-otoresist, for example, a resin composition obtained by adding a photo-crosslinking agent such as a diazo compound to an acrylic or polyvinyl alcohol-based polymer, or a photo-crosslinking group such as chalcone or cinnamic acid. A method is employed in which a resin composition, etc., in which acrylic or polyvinyl alcohol-based polymer is introduced in advance, is dissolved in water or an organic solvent, applied by spin coating, and cured by irradiation with ultraviolet rays.

In the present invention, glass, plastic sheets, silicon wafers, etc. can be used as substrates on which the coating to be dyed is provided, after being pretreated with a silica/coupling agent, etc., or provided with a flattening layer, if necessary. be done.

Example The present invention will be explained in more detail by way of Examples.

Example 1 Optical glass (a high-purity glass plate with excellent light transmittance) K CFR-633L (acrylic anionic dye-dyeable photosensitive resin composition manufactured by Nippon Kayaku) was coated by spin coding. After drying at 80°C for 30 minutes, UV irradiation with a surface illuminance of 8 mw/crd was performed for 5 seconds through a mask with a pattern, and Emuldan 913 (manufactured by Kao Soap ■, polyoxyethylene 7 nonylphenol ether type nonionic interface? 1tJI) was applied. 6 containing 2 parts per 1000 parts of water
When development was performed for 5 minutes with stirring in a developer at 0'C, a glass substrate having a dyeable film only in the irradiated area was obtained. After this glass plate was further post-baked at 160° C. for 30 minutes, the film thickness was 0.5 μm. This glass plate is immersed in a dye bath in which the compound of formula (II) is dissolved in water to a concentration of 0.2%,
Staining was carried out at 60° C. for 10 minutes, resulting in a blue pattern.

When the spectral transmittance curve of the blue colored part was measured, it was 600
The transmittance in the vicinity of nm was 1% or less, and the wavelength at which the transmittance was 50%, λT=50%, was 492 nm.

Ultraviolet cut filter (manufactured by HOYA Co., Ltd., -4
Optical density (-IogT) at the maximum absorption wavelength of the blue colored part when exposed to light for 80 hours using a standard fade meter (FAL-3H model manufactured by Suga Test Instruments)
The reduction rate was 2%, and there was almost no fading.

The compounds used in this example are shown below.

Comparative Example The spectral transmittance # line of the blue colored part of a colored glass plate prepared by the same method as in Example 1 except that the dye C0I and Acinodo Blue 62 were used was similar to the curve obtained in Example 1. When the light fastness test shown in Example 1 was carried out, the color changed significantly to red, and the color could no longer be called blue.

Example 2 A glass plate on which a resin was placed in a pattern obtained by the same operation as in Example 1 was coated with 0.25% of the compound of formula (11).
% aqueous solution at 50° C. for 15 minutes to obtain a glass plate colored in a blue pattern. When we measured the spectral transmittance curve of the blue colored part, we found that the transmittance in the region of 600±3Qnm was the wavelength at which the transmittance was 50%, λ, under high yield.
T=50 was 493 nm.

The colored glass plate was heat-treated at 180°C for 1 hour in the open, and after cooling, the transmittance at the maximum transmission wavelength of 450 nm (T
%) was measured and found to be 1.2%, indicating almost no fading.

Comparative Example 1 The blue colored portion of a blue glass plate prepared by the same method as in Example 1 except that the dye was replaced with C11 and Acinodo Blue 90 had a maximum transmission wavelength of 465 in the heat resistance test shown in Example 2.
The rate of decrease in transmittance at 1 m was 36.5%, and the color was significantly faded.

Example 3 A glass plate on which a resin was placed in a pattern obtained by the same operation as in Example 1 was mixed with compound 50 of the formula (Ill) and the formula (
5 in a 0.3% aqueous solution of a mixture consisting of 50 button compounds.
Staining was carried out at 0°C for 20 minutes to obtain a glass plate colored in a blue pattern.

When the spectral transmittance curve of the blue colored part was measured, it was 570
The transmittance in the S630 nm region was 1% or less, and the wavelength showing the maximum transmittance of 65% was 4451 m.

The colored glass plate was heat-treated at 200°C in the open for an IQ period, and after cooling, the transmittance at the widest transmission wavelength of 4501 m (T%
) was measured and found to be 6.8, which was within the allowable range.

Comparative Example 2 The blue colored portion of a blue glass plate prepared by the same method as in Example 1 except that the dye was replaced with C, I, and Asindo Blue 90 had a maximum transmission wavelength of 465 in the heat resistance test shown in Example 3.
The rate of decrease in transmittance at 1 m was 61.4%, and the color was significantly faded.

Example 4 On optical glass, 8 parts of ammonium dichromate was added to 4 parts of FCR-500 (manufactured by Fuji Pharmaceutical Co., Ltd., gelatin aqueous solution).
A photosensitive liquid mixed with 1 part of % aqueous solution and defoamed was applied to a film thickness of lμ by a spin code method, prebaked at 80°C for 10 minutes, and passed through a mask with a predetermined pattern to a mask alignment device MA. -Type 10 (Mikasa ■
After exposure with an energy amount of 300 millijoules/7 using a commercially available commercially available product (manufactured by J.D. Co., Ltd.), the film was developed in hot water at 400C. Then 120°C
The gelatin film was post-baked for 10 minutes to harden the gelatin film.

Next, 0.0% of a mixture of compounds of formulas (n) and (It) adjusted to pH 5 with acetic acid in a ratio of 60:40 was added.
After immersing in a 2% aqueous solution at 60°C for 5 minutes and washing with water, immersing in a bath consisting of 0.3% high tannic acid (manufactured by Inunippon Seiyaku ■) and 0.2% acetic acid at 70°C for 5 minutes, washing with water, Next, it was immersed in a 0.5% aqueous solution of Niepaflon (fixer manufactured by Dainippon Pharmaceutical Co., Ltd.) at 70° C. for 5 minutes, washed with water, and dried to form a first blue colored layer.

Next, a photosensitive gelatin layer was provided in the same manner as described above, exposed and developed, and immersed in a 0.5% aqueous solution of Acid Red 317 at 60 ° C. for 10 minutes. After dyeing, a fixing resist dyeing treatment was applied in the same manner as described above to provide a second red colored layer.

Next, another part of the gelatin layer is coated with CFG as described above.
-5IP (Nippon Kayakuen color filter dye) 0
．． After dyeing in a 5% aqueous solution at 60'C for 15 minutes, a fixation resist treatment was applied to form a third green colored layer. It should be noted that no elution of the blue dye into the tannic acid bath and the fixing bath which were subjected to the fixation resist dyeing treatment three times was observed.

The obtained color filter consisted of three colors, blue, red, and green, and was suitable for use in liquid crystal color televisions. When the spectral transmittance curve of the blue colored part was measured, the transmittance in the region of 570 to 630 nm was less than 1.
Wavelength 1 showing 50% transmittance. (7=5Q%, is 4921
It was m.

Also, dirt fade meter (FA made by Suga Test Instruments)
Maximum transmission wavelength 4 after 100 hours of exposure to L-3H type)
The rate of decrease in transmittance (T%) at 5 Q nm was 2%, and the color was almost fading.

Comparative Example Blue dye C01 used to obtain the first blue colored part
, The spectral transmittance curve of the blue colored part of the color filter produced by the same method as in Example 4 except that Acid Blue 62 was used was similar to that in Example 4, but the results of the light emission test described in Example 1 However, there was no need to measure the spectral transmittance curve, and there was a marked red discoloration.

Effects of the invention A color filter with a blue colored film that has color characteristics, light emission, and heat resistance by using a water-soluble anthracite compound or a mixture thereof represented by a specific formula as a blue dye for color filters. Now I can do it.

4,

[Brief explanation of drawings]

In Fig. 1, (a) shows the substrate (glass plate), fb) shows the glass plate provided with the photocurable thin film, and (C) shows the step of irradiating the photocurable thin film with ultraviolet light through a photomask. , (d) is the glass plate provided with the colored layer, (91 is the step of dyeing the colored layer, (f) is the step of providing a non-stainable protective film on the colored layer, (g) 1 represents the step of providing a second colored layer, and (h) represents the step of providing a second non-staining protective film.In addition, in FIGS. 1(a) to (h), 1 glass plate 2 photocurable Thin film 2' Colored film 2'' First colored layer 3 Non-staining protective film 47 Otomask 5 Second colored layer 6 Non-staining protective film 7 Developing tank 8 Dyeing tank 9 Irradiation lamp.

Claims (1)

[Claims] 1. A color filter in which a patterned colored film is placed on a substrate, in which at least one pattern is colored with a water-soluble anthraquinone compound represented by the following formula (1) or a mixture thereof. A color filter characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In formula (I), X and Y are each independently H or ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ and M are H, Na, K,
Li, NH_4NH_3CH_2CH_2OH, NH_
2(CH_2CH_2OH)_2 or NH(CH_2C
H_2OH)_3 respectively. ]