JPH03219201A - Color filter - Google Patents

Abstract

PURPOSE:To obtain good reproducibility in a yellow region and excellent optical characteristics by coloring patterns with a specific compd. CONSTITUTION:The patterns of the color filter formed by imposing films colored to pattern shapes are colored by the compd. expressed by formula I. In the formula, R1 denotes NH2, OH; R2, R3, R4 denote H, halogen atom, SO3M (M is H, Na, K, Li, NH4, etc.); n is 1 or 2; D is the group expressed by formula II. The yellow dye for the color filter which is adequate in dyeability, is hardly decolorable and has the desired optical characteristics 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, and sensors.

The conventional dyeing method for manufacturing color filters involves coating the surface of a substrate such as glass or silicon wafer with a thin film of transparent synthetic resin having cationic groups in the form of stripes or mosaics (called a pattern). A coat of protein-based natural polymer substances such as gelatin, casein, and 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.

(υ After a film to be colored is provided on the surface of the substrate, it is exposed through a mask and developed, and the resulting pattern is dyed to form a colored layer.Next, a non-colored protective coat film is provided on the entire surface, and this A second coat to be colored is provided on top by the same operation as 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.

(3) A film to be colored (a colored film) is provided on the surface of the substrate. After a positive resist layer is provided thereon, the colored film exposed in a pattern is dyed by exposure and development through a mask, and then the positive resist layer is peeled off to form a colored portion. Repeat the operations after forming the positive resist layer,
The same colored film is dyed in multiple colors in a desired pattern.

Color filters manufactured by the above process usually have three primary colors: R (red), G (J'&),
B (blue) or three complementary primary colors YCfi+)-M(
It has a colored layer colored in magenta) and C (cyan). The most important property required of a color filter is its optical property, and the spectral properties of each colored layer greatly control the value of the final product. By the way, since protein-based natural polymer substances such as gelatin, casein, 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, water-soluble anionic dyes can be used in the same way as protein-based natural polymer substances. Becomes stained.

By the way, in order to obtain optical properties desired as a color filter, a large number of water-soluble anionic dyes have been studied singly or in combination. However, in the case of complementary yellow, it is difficult to select a dye that has good dyeability, desirable optical properties, and excellent reliability (light resistance, heat resistance), and at present no dye that is satisfactory has been found. do not have.

The desired optical properties are 50% of the dyed colored film.
When two wavelengths that give transmittance = 50% are matched to a predetermined wavelength (generally 480 to 570 nm), 550 nm to
The length is high enough to have a transmittance of 700 nm, preferably 8
0% or more, and the length is small enough to provide transmittance at 450 to 400 nm, preferably 1% or less.

Conventional yellow dyes for color filters include C, I-
Dyes such as Ac1d yeIJow 236 (7) have been used as complementary color yellow dyes and as primary color green correction dyes, but their dyeing properties are not appropriate and they are easily bleached, so they do not have the desired optical properties. This is difficult to obtain and is a major impediment to practical use.

Problems to be Solved by the Invention Desired optical properties and reliability (mainly,
A number of water-soluble anionic dyes have been investigated in order to obtain dyes with excellent resistance to heat and light. As mentioned above, the optical properties required for a complementary color yellow dye are such that the wavelength λT = 50% that gives 50% transmittance of the dyed colored film is a predetermined wavelength (generally 480 to 52
Qnm), 550nm to 7o.

The length is high enough to have a transmittance of 450 nm to 400 nm, preferably 80% or more, and the transmittance of 450 nm to 400 nm is as low as possible, preferably 1% or less. There is a strong desire to develop a yellow dye for color filters that has desired optical properties.

Means for Solving the Problems The inventors of the present invention made earnest efforts to find a color filter having the optical properties as described above, and as a result, it was found that a color filter dyed (colored) with a specific compound has the optical properties as described above. The present invention has been achieved by finding that the above conditions are satisfied. That is, the present invention is characterized in that in a color filter in which a patterned colored film is placed on a substrate, at least one pattern is colored with a compound represented by the following formula (1) or a mixture thereof. Provide color filters.

In formula (1), R1 is NH2 or OH, R21
R3 and R4 each mean H, a halogen atom, or SO3M (M means H, Na, K + Li+ NH41 monoethanolammonium, jetanolammonium, or triethanolammonium).

n is 1 or 2, and D is (M has the same meaning as above) (1-C).

However, when D is formula (1-C), R1 in formula (1) means NH2.

Also, when D is formula (1-A) or (1-B),
R2 in formula (1). Any one of Rs and L means S03M (M has the same meaning as above).

In formula (1), when D is formula (1-A),
Disazo dyes are made by known methods. That is, the azo component represented by is diazotized with sodium nitrite and hydrochloric acid in a conventional manner, and then 'Jffringed with phenylpyrazolone having a substituent (formula (1-D)) to obtain a disazo dye of formula (1). is obtained.

The mono- or disazo dye of formula (1) obtained by bubbling is subjected to solid-liquid separation using sodium chloride or the like. Then, if necessary, after acidification treatment and ion exchange treatment to remove metals, caustic soda, lithium hydroxide, caustic potassium, ammonia, monoethanolamine, jetanolamine, or a. Formula (1-B) or (1-C
), after diazotizing a known monoazo dye using sodium nitrite and hydrochloric acid,
Coupling with a phenylpyrazolone having a substituent (formula (1-D)) yields a monoazo dye of formula (1).

In either case, ka is used.

Next, an example of the color filter of the present invention will be explained using the drawings. FIGS. 1(a) to 1(h) are schematic diagrams showing a method for manufacturing a color filter of the present invention in which colored layers of different colors are laminated on a glass plate (substrate) (layering method). In Fig. 1, 1 is a glass plate, 2 is a thin film of photocurable 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, and 3 is a thin film of photocurable resin etc. non-staining protective film,
4 is a photomask, 5 is a second colored layer, and 6 is a non-stainable protective film.

First, on a glass plate 1, a mixture of a protein-based natural polymer such as gelatin, casein, or glue and a dichromate such as ammonium dichromate or a photocurable synthetic resin composition having a cationic group is coated with Laspin; Apply by a method such as roller coating to a thickness of 0.2 to 2
A photocurable thin film 2 of μ is provided (FIG. 1(b)).

Next, a photomask 4 having a predetermined pattern on the thin film
The exposed area is cured by irradiating it with ultraviolet light. (1st
Figure (C)) Next, the unexposed areas are removed by developing with water or the like for 11 to 10 minutes at 15 to 60°C to form a colored layer 2' in a predetermined pattern. (d)), dyeing with a dye having predetermined optical properties to obtain a first color to form a first colored layer 2'' (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 is exposed to light through a mask and developed to form a colored layer in a predetermined pattern. ,
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 over the entire surface (Fig. 1).

This operation can be repeated to form a colored layer of a third color and further a colored layer of a fourth color.

In a direct-mounted color separation color filter for a solid-state image sensor or a color separation filter, a flattening layer is provided on a silicon wafer, which serves as a base, on which a light detection section etc. are provided.
A colored layer can be formed thereon by the same operation as described above, and the same material as the non-staining protective film can be used as the leveling layer.

The colored layers are primary colors R (red), G (green), and B (blue).
In some cases, complementary colors Y (yellow), M (magenta),
A case of C (cyan) is also possible. Green can also be obtained by combining yellow and cyan, forming a yellow colored layer and a cyan colored layer, or dyeing it yellow or cyan and then dyeing it again with cyan or yellow dye2. It can also be formed by a double dyeing method.

In the present invention, the compound represented by the formula (1) or a mixture thereof is used as a dye to obtain a complementary color Y (yellow) colored layer, and the yellow colored layer has good spectral transmission characteristics. Therefore, it is possible to obtain faithful color reproducibility as a color separation color filter, and it is also possible to obtain a color image with good color balance as a display color filter.

Protein-based natural polymer substances such as gelatin, casein, and glue that are to be colored in the present invention will be explained. Gelatin is an animal protein made by boiling collagen with water to irreversibly make it water-soluble. Gelatin is extracted from animal bones, skin, arms, etc. by boiling it with water. Casein is a phosphorus protein that is the main component of milk. After uniformly coating a substrate such as glass using these top roller coating methods, the coating layer is cured by irradiation with ultraviolet rays, and then processed (developed) in water for 1 to 10 minutes at 10 to 60°C to form a pattern. The cured film can be changed.

Further, examples of synthetic resins having a cationic group as a coloring material used in the present invention include the following.

That is, a base material is prepared using a photoreactive resin composition consisting of an anionic dye-dyeable polymer, a compound having two or more photoreactive unsaturated groups in one molecule, a diazide photosensitive compound, and optionally an organic solvent. After being applied to the surface, active light such as ultraviolet rays is irradiated to cause a reaction and form a film. In this case, the anionic dye-dyeable polymer is, for example, (N,N-dimethylamino)ethyl acrylate, (
It is obtained by polymerizing a nitrogen-containing monomer such as N,N-diethylamine) ethyl methacrylate, a hydrophilic monomer such as hydroxyethyl acrylate or dimethylamino acrylamide, and a hydrophobic monomer such as methyl acrylate or butyl methacrylate. Examples of compounds having two or more photoreactive unsaturated groups in one molecule include ethylene glycol diacrylate and diethylene glycol diacrylate.

Further, as a diazide photosensitive compound, for example, 4゜4'-
Examples include diazidochalcone, 2,6-bis(4'-azidobenzal)cyclohexanone, and the like.

As the organic solvent used for diluting the resin composition, for example, methyl cellosolve, methyl ethyl ketone, toluene, etc. are used alone or in a mixed system.

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

Examples of photocurable anionic dye-dyeable synthetic resins are not limited to the above examples, and include polymers having photoreactable unsaturated groups and quaternary ammonium bases in their side chains as main components. A photoreactive resin composition consisting of a photopolymerization initiator and a solvent, or a cationic group-containing polymer in which a photocrosslinking group such as chalcone, cinnamic acid, azide, or stilbazole group has been introduced into the polymer is added to water or an organic solvent. A dissolved resin composition may also be used.

To dye (color) the cured film using the 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, usually 0.1 to 30 g, preferably 1 to 10 g of the compound of formula (1) is dissolved in 12 of water at a temperature of 10 to 100°C. After soaking for about a minute, take it out, wash it with water, and dry it. The yellow film thus obtained exhibits optical properties suitable for use as a color filter.

The non-staining protective film can be provided using a negative photoresist, such as a resin composition obtained by adding a photocrosslinking agent such as a diazo compound to an acrylic or polyvinyl alcohol polymer, or a photocrosslinking 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 to be provided, after being pretreated with a silane coupling agent or the like or provided with a flattening layer as necessary. be done.

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

Example 1 1 part of an 8% aqueous solution of ammonium dichromate was mixed with 4 parts of FCR-500 (manufactured by Fuji Pharmaceutical Co., Ltd., gelatin aqueous solution) on optical glass (a high-purity glass plate with excellent light transmission). The degassed photosensitive liquid is processed to a film thickness of 1 by spin code method.
After pre-baking at 80℃ for 10 minutes, a mask alignment device MA-10 model (manufactured by Mikasa ■) was used to apply the coating to 30℃.
After exposure with an energy amount of 0 mJ/cm”, 4
Developed in warm water at 0°C. The gelatin film was then post-baked at 120° C. for 10 minutes to harden the gelatin film.

Then, 0 of the compound of formula (2) adjusted to pH 4 with acetic acid.
．． It was immersed in a 5% aqueous solution at 60°C for 10 minutes, washed with water, and dried to form a first yellow colored layer.

Next, FVR-GIO (manufactured by Fuji Pharmaceutical Co., Ltd., oil-soluble negative photoresist) was applied using a spin code method to a film thickness of 0.5μ, prebaked at 120°C for 10 minutes, and then exposed to an ultra-high pressure mercury lamp. Used 55/mW/Cm2
After rinsing, the film was subjected to a post-baking at 150° C. for 20 minutes to form a resist dyeing layer.

Next, a photosensitive gelatin layer is provided on this resist layer in the same manner as described above, exposed and developed to form a dyeable layer with a specific pattern, and p)l is converted to 5 with acetic acid. A compound of the following formula (3) was prepared.

CZn Pc stands for zinc phthalocyanine. p-1゜q
=00 compound as main component, p=q=1; p=2゜q
=0; p-2, q-1; p=3. q=0; p=1. q-
2: p=x, (1=3; p=(1=2: p
-3, q=i; I)=4, a mixture containing a compound where q=O as a trace component. λma in water
x 632 nm] for 5 minutes at 60° C. to form a second colored layer.

Next, the same photosensitive composition as the resist layer described above was spin-coded to a thickness of 05 μm, and exposed under the same conditions to form a protective film.

Next, a photosensitive gelatin layer was provided on this resist dye layer in the same manner as described above, exposed and developed to form a dyeable layer with a specific pattern, and the pH was adjusted to 5 with acetic acid. The third colored layer was immersed in a 062% aqueous solution of the compound of formula (3) below at 60°C for 5 minutes, and then the same photosensitive composition as the above-mentioned resisting layer was spun to a thickness of 0.5μ. A protective film was formed by exposing to light under the same conditions. The resulting color filter consisted of three colors, yellow, magenta, and cyan, and was suitable as a color filter for solid-state imaging devices.

In addition, when the spectral transmission curve of the yellow colored part was measured, it was found that 50
The wavelength that gives % transmittance is 507nm and 55Qnm
The transmittance at ~7QQnm is over 90% and 45Q
The transmittance between nm and 400 nm was 1% or less.

Moreover, each yellow colored part was uniformly dyed and had the same spectral transmission curve.

Figure 2 shows its spectral and transmission curves. Moreover, the heat resistance and light resistance were also excellent.

Comparative Example The yellow dyes used to obtain the first colored layer were C, I A
Example 1 except that c1d Yellow 236 was used.
The yellow colored parts of the color filter produced by the same method as above were not uniformly dyed, and the desired spectral characteristics could not be obtained.

Example 2゜Dimethylaminopropylacrylamide 31 parts 2-hydroxyethyl methacrylate 14
Part Vinylpyrrolidone 15
methyl methacrylate
15 parts methyl acrylate
13 parts dimethylamine acrylamide
10 parts dioxane
200 parts α,α-azobis(isobutyronitrile)
After polymerizing 1 part of the above liquid at 80°C in a nitrogen atmosphere for 5 hours, the polymer solution was poured into a large amount of Improvil ether to precipitate the polymer, and the polymer was taken out and dried. . This dry polymer 1
5 parts, 0.63 parts of 4.4'-diazide chalcone, 0.57 parts of spiroglycol diacrylate, 88 parts of ethyl cellosolve, and 27 parts of diethylene glycol dimethyl ether.
A dyeable photosensitive resin liquid was prepared by mixing and dissolving 0.6 parts of a silane coupling agent KBM603 (Shin-Etsu Chemical Co., Ltd.).

Next, this is coated on a glass plate using the spin code method.
After drying at 80°C for 30 minutes, UV irradiation was performed for 5 seconds at a surface illuminance of 8 mw/am2 through a mask with a resolution test pattern, and Emulgen 913 (manufactured by Kao Soap ■, polyoxyethylene nonylphenol ether type nonionic surfactant) was applied. When development was carried out for 5 minutes with stirring in a developer at 60° C. containing 2 parts of water per 100 parts of water, a glass substrate having a dyeable film only in the irradiated area was obtained. This glass plate was further post-baked at 160°C for 30 minutes. This glass plate was immersed in a 0.5% aqueous solution of a compound of formula (5) whose pH was adjusted to 4 at 60'C for 10 minutes to obtain a yellow colored layer colored in a pattern.

When the spectral transmittance curve of the colored part was measured, each yellow colored layer was colored uniformly, and the wavelength that gave 50% transmittance was 510 nm, and the transmittance from 55-0 to 700 nm was 90%. As above, the transmittance at 450 to 500 nm was 0.5% or less, and the yellow color filter exhibited desirable optical properties as a complementary color filter.

Minimum transmission wavelength: 432 nm Examples 3 to 7 The yellow dye used to obtain the first colored layer was expressed by the following formula (6
The yellow colored portion of the color filter prepared by the same method as in Example 1 except that the compounds of ) to (10) were used had the optical properties and light resistance required for the yellow color described above, and was suitable for solid-state imaging devices. This was desirable as a color filter for use in industrial applications.

Minimum transmission wavelength: 438 nm Minimum transmission wavelength: 437 nm As a color filter for displaying the effects of the invention, the color filter has good reproducibility in the yellow region and exhibits excellent optical properties and durability.

[Brief explanation of drawings]

In Figure 1, fa) is the substrate (glass plate), (b) is the glass plate provided with the photocurable thin film, and FC) is the process of irradiating the photocurable thin film with ultraviolet light through a photomask. , (d) is the glass plate provided with the colored layer, (eJ is the step of dyeing the colored layer, (f) is the step of providing a non-stainable protective film on the colored layer, (gJ is the step of dyeing the colored layer) 2 represents the step of providing a colored layer, and (h) represents the step of providing a second non-staining protective film.In addition, in FIGS. 2' Colored film 2' First colored layer 3 Non-staining protective film 4 Photomask 5 Second colored layer 6 Non-staining protective film 7 Developing tank 8 Dyeing tank 9 The irradiation rank is shown respectively. The spectral transmission curve of the color filter obtained in Example 1 is shown.

Claims (1)

[Claims] 1. In a color filter in which a patterned colored film is placed on a substrate, at least one pattern is colored with a compound represented by the following formula (1) or a mixture thereof. Characteristic color filter. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) In formula (1), R_1 is NH_2 or OH, R
_2, R_3, R_4 are H, halogen atoms or SO_3
M (M means H, Na, K, Li, NH_4, monoethanolammonium, diethanolammonium or triethanolammonium), respectively. Also, n is 1 or 2, and D is: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1-A) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1-B) or ▲ Mathematical formulas, chemical formulas, tables, etc. etc. ▼ (M has the same meaning as above) (1-C). However, when D is formula (1-C), R_1 in formula (1) means NH_2. Furthermore, when D is formula (1-A) or (1-B), any one of R_2, R_3, and R_4 in formula (1) is SO_3M (M has the same meaning as above). .) means.