JPH02302701A - Production of coloring material for color filter and production of color filter - Google Patents

Abstract

PURPOSE:To obtain a high accuracy color filter by allowing an acidic soln. of a titanium (IV) acetylacetonato complex (1:2) to react with a naphthalene or anthraquinone compd. in a prescribed ratio. CONSTITUTION:An acidic soln. of a titanium (IV) acetylacetonato complex (1:2) is allowed to react with a naphthalene or anthraquinone compd. in a prescribed ratio. Satisfactory adhesion of the complex itself is utilized, the hydrolysis of the complex with water on the surface of a filter is inhibited because of the acidic soln. and this soln. is prevented from getting cloudy. A coloring material is formed by allowing the acidic soln. of the complex to react with the naphthalene or anthraquinone compd. The formed coloring material is of non-polymer type, has color developing and spectral properties comparable to those of a polymer type coloring material and can ensure tight adhesion. The resulting color filter has satisfactory adhesion of the coloring material itself and enhances pattern accuracy and positional accuracy.

Description

Detailed Description of the Invention (Industrial Application Field) This invention relates to a color filter color filter used in color separation color filters necessary for full-color liquid crystal displays and solid-state imaging devices (hereinafter referred to as CCDs). Regarding materials.

(Prior technology) Recently, various superior technologies such as low voltage, low power drive, miniaturization, and flatness have been developed for color televisions that use conventional CRTs and video cameras that use image pickup tubes. The development of LCDs and CODs that offer these advantages is underway. In particular, the color filters used for colorizing LCDs and CODs are undergoing various changes as LCDs become larger and CCDs become more precise. The formation method is being studied.

This color filter has R (red) and G as each picture element.
It is constructed by arranging three colors (green), B (blue), and complementary colors (only in the case of CCD) in a matrix or stripe pattern. For example, in the case of a color filter for a liquid crystal display, the size and interval of this picture element is 1.
00 μm 1 interval is 10 μm or more, and in the case of a color filter for CCD, the size is 15 μm 1 interval is 2 μm or less.

At present, methods for forming these picture elements mainly include a dyeing method, a printing method, an interference film method, and the like.

The dyeing method involves forming a fine pattern of the material to be colored in stripes or mosaics on a glass substrate by applying photolithography, and then dyeing it with a dye having predetermined spectral characteristics to obtain a colored pattern. It is. The colored layer used at this time is usually a water-soluble polymer such as gelatin, which is a natural product, and a photosensitizing agent added to it. A polymer material is formed as a protective film.

The advantages of this dyeing method include good pattern accuracy and positional accuracy, a wide selection of colors, and relatively good spectral characteristics.

The printing method is a method of printing a color pattern on a glass surface using a coloring material using pigments by offset printing or screen printing.

The advantages of this printing method are that it uses pigment-based coloring materials, so it has improved heat resistance and light resistance, and a wide range of colors to choose from.
It is suitable for mass production and can reduce costs. Therefore, this is one of the most anticipated methods for forming picture elements in response to the increasing screen size of liquid crystal displays.

The interference film method uses a high refractive index material and a low refractive index material.
The color filter is formed using the principle that when /4 wavelength plates are stacked alternately, the spectral transmittance becomes closer to a rectangle as the number of layers increases.The color filter formed by this interference film method is a dielectric film. It is a type of interference filter with a multilayer film structure, and is currently used as a color separation filter for single-tube color image pickup tubes.

The advantages of the color filter formed by this interference film method are that the material is inorganic, so it has very good spectral transmittance, and the spectral properties can be sharpened, so it has excellent color separation, and it has excellent heat resistance, chemical resistance, etc. It has excellent durability, etc.

(Problems to be Solved by the Invention) However, the method for forming each picture element described above has the following problems.

In other words, although the dyeing method has the above advantages,
The problem is that the manufacturing process is long and expensive, and the gelatin used as the coloring layer is a natural product.
The problem is that there are large variations in characteristics, which is a major obstacle in terms of quality and cost.

In addition, in the case of printing, although it has the above-mentioned advantages and is very useful, since it uses pigment-based coloring materials, black spots may occur due to poor pigment dispersion, and dimensional accuracy may be poor. Moreover, there were problems in that the film thickness became thick and the spectral transmittance also deteriorated.

Furthermore, in the case of color filters formed by the interference film method, although they have the same advantages mentioned above, it is very difficult to control the thickness of the interference film, and the larger the color filter, the more expensive it becomes, resulting in high costs. This has become a big problem, and in terms of quality, it has often been used only for applications that cannot be achieved using other methods.

Therefore, with the current manufacturing technology for color filters using the main picture element formation methods, it has not been possible to provide highly accurate color filters or achieve a satisfactory cost reduction. Rapid development was desired to meet the demand for CCDs and CCDs.

Therefore, in view of the above-mentioned problems, the present invention was created with the aim of providing a highly accurate color filter, a coloring material most suitable for cost reduction, and a method of manufacturing a color filter using the same. It is.

(Means for Solving the Problems) This invention involves reacting an acidic solution of titanium (IV value) acetylacetonate complex (1:2) with either a naphthalene compound or an anthraquinone compound in a predetermined ratio. In addition, for color filters formed by reacting an acidic solution of titanium (IV value) acetylacetonato complex (1:2) with either a naphthalene compound or an anthraquinone compound in a predetermined ratio. By forming a color pattern on the surface of a predetermined translucent plate material using a coloring material, titanium (IV value)
A coloring material for a color filter formed by reacting an acidic solution of an acetylacetonate complex (1:2) and an anthraquinone compound in a predetermined ratio is appropriately coated or printed on the surface of a predetermined translucent board material, and then, The above-mentioned problem is solved by irradiating ultraviolet rays and developing to form a color pattern.

(Example) The present invention will be explained in detail below.

That is, first, a titanium (TV) acetylacetonato complex (1:2) is produced.

This titanium(IV) acetylacetonato complex (1:2)
is produced by reacting titanium (IV) isopropoxide and acetylacetone at a molar ratio of 1:2.

Next, acetic acid was added to the titanium (IV) acetylacetonato complex (1:2) reaction product thus produced, and at that time, isopropyl alcohol was added as a solvent to form the titanium (TV) acetylacetonato complex. (1:2) treatment liquid (hereinafter referred to as TAA treatment liquid) is prepared.

The composition at this time was: titanium (IV) acetylacetonate complex (1:2)
0 ml isopropyl alcohol (IPA) 60 ml acetic acid (CH3C00H) 1.5 ml.

It goes without saying that the blending ratio of this TAA treatment liquid is not limited to the above-mentioned values.

Either a solution of a naphthalene compound or a solution of an anthraquinone compound is added to the TAA treatment solution thus prepared at a volume ratio of 1:1 and reacted to produce a solution as a coloring material. It is something.

To explain this production process and the color filter manufacturing experiment using it in more detail, titanium (22-3d
2-432) has an empty d orbital that requires the acceptance of eight electrons in the 3d orbital, and exhibits unique behavior because it has two 3d electrons. Therefore, it is known that, for example, chelate compounds are formed with compounds such as 1,3-glycol, β-di)rton, salicylic acid, and catechol. Since titanium has a maximum coordination number of 6, up to three atoms can be bonded to one titanium atom in a configuration that allows bonding to titanium at two locations.

Therefore, T i (OR) 4 and acetylacetone,
]:1 is known to produce a chelate compound as shown in the following formula, namely titanium (IV value) acetylacetonato complex (hereinafter referred to as TAA) (YAMAMOTO, KANBAI?A report).

T i (OR)4 +CH3CCH-CCH3→1
1] HO Utilizing such a relationship, TAA was synthesized and used by reacting tetraisopropyl titanate (T P T) in which R is C or H7 with acetylacetone at a molar ratio of 1:2.

And, as mentioned above, T AA 40m1
A TAA treatment solution was prepared by mixing 80 ml of isopropyl alcohol (IPA) and 1.5 ml of acetic acid (CH, C00H).

A naphthalene compound or anthraquinone compound as a color developer shown below is added to this TAA treatment solution.

The naphthalene compound is α-naphthol (manufactured by Tokyo Kasei Kogyo, first class reagent) C+oH
s 0-144.17 mp 96.1°C, bp 285-286°C Colorless columnar product, sublimable, easily soluble in base solvents, slightly soluble in water, mainly synthetic raw material for dye intermediates.

β-Naphthol (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd., first class reagent) C4゜H
3O-144,17 mp 123℃, bp 285-286℃ Colorless to slightly yellow plate-like or needle-like crystals, sublimable, easily soluble in base solvents, poorly soluble in water,
Basic intermediates such as naphthol dyes and chromium dyes.

1.2-Naphthalenediol (manufactured by Aldrlch Chew, super special reagent) CIOH
802=160.17 mp103-104°C Colorless needle-like crystals (carbon disulfide), dissolves in alkaline aqueous solution to give a yellow color, but turns green in air.

It is oxidized by iron chloride (DI) to form 1,2-naphthoquinone. When mixed with benzoquinone, 1°2-naphthoquinone and hydroquinone are produced.

1.3-naphthalene diol (Manufactured by Tokyo Kasei Kogyo, super special grade reagent) CIOH802””160. 17 mp　124℃ Soluble in water.

1.4-Naphthalenediol (manufactured by Tokyo Kasei Kogyo, special grade reagent) C+oHs 02'' = 160.17mp195℃ Colorless long needle crystals, easily soluble in ethanol, ether, acetic acid,
It is quite soluble in hot water and easily becomes 1,4-naphthoquinone when oxidized with chromium (VI) oxide. Antioxidant.

1.5-naphthalene diol (Manufactured by Tokyo Kasei Kogyo, first class reagent) C0゜H,0□-160,17 mp260℃ Dissolved in acetone, acetic acid 1.6-naphthalene diol (Manufactured by Tokyo Kasei Kogyo, special grade reagent) C0゜H802-160,17 mp137-138℃ Sublimable, soluble in benzene and acetone 1.7-Naphthalene diol (Manufactured by Tokyo Kasei Kogyo, super special grade reagent) C1゜H, 0□-160', 17 mp181.5℃ Sublimable, soluble in water and ethanol 2.3-Naphthalene diol (Manufactured by Tokyo Kasei Kogyo, special grade reagent) C1゜H802-160,17 mp163.5-164℃ Sublimation point 150~160℃ Purified by sublimation, irritating, azo dye synthesis intermediate.

2.6-naphthalenediol (manufactured by Aldrlch chem, super special reagent) C,0H
802-160,17 mp218℃ Sublimation, soluble in ethanol 2,7-naphthalene diol (manufactured by Wako Tsumugi Kogyo, special grade reagent) C+oHs 02-160. 17 mp 194°C Sublimable, ethanol-soluble anthraquinone compounds include: 1,2-dihydroxyanthraquinone (manufactured by Wako Tsumugi Kogyo, special grade reagent) C14H1304-240, 20 mp 290°C, bp 43Q°C, sublimation point 1 0°C Orange-red plate-shaped and needle-shaped crystals, easily soluble in hot methanol and ether.

Use: Red dye.

1.4-Dihydroxyanthraquinone (manufactured by Tokyo Kasei Kogyo, special grade reagent) CI4H1304-240, 20 mp 194-195°C Yellowish red crystals or red crystals, soluble in ether, quinone dye intermediate.

1.8-Dihydroxyanthraquinone (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd., special grade reagent) C14H1304'' 240, 20mp191°C Yellowish red crystals, soluble in ether, anthraquinone dye intermediate.

And so.

Micro cover glass (MATS) was used as a substrate.
UNAMI GLASS IND, LTD.) 40
The surface of this substrate was cleaned through alkaline degreasing and ultrasonic water washing to ensure a clean state.

Next, the above color developer was added to the TAA treatment solution and reacted.

As a color developer, TAA's color-forming reaction is said to be effective when it reacts with aromatic compounds to which an OH group is added as a substituent. Although similar reactions have been reported, we selected a compound with a strong resonance system for the purpose of producing a more bathochromic reaction than this reaction color. In addition, each isomer was selected in order to investigate the change in color tone due to the influence of the position of these substituents. Therefore, the above-mentioned naphthalene compound or anthraquinone compound was selected as the color developer.

Since various conditions such as adhesion, film formability, and reaction ratio are important, we adopted the liquid coloring dye coating method in which the generated coloring material is applied to the substrate as described above. I went there and manufactured color filters.

As a result, we were able to obtain the following data.

That is, the film thickness of the coloring material on the substrate is, for example, 0.6
The dominant wavelength of each reaction benthic organism in μm is shown below.

Color developer name Main wavelength α-naphthol 577.0n
Meng β-naphthol 572.0
rv.

1.2-Naphthalene diol 591. Onm
l,3-naphthalene diol 589. Onm
l,4-naphthalene diol 650. On layer 1.5-naphthalene diol 591.5Hm
1.5-hexaphthalenediol 5H,5Hm
1.7-naphthalenediol 5g8.5n
112,'3-naphthalene diol 582.
0ni2.6-naphthalene diol 594
．． 0rv2.7-naphthalene diol 57
7.5Hm1.2-dihydroxyanthraquinone 6
18. Or++w1.4-dihydroxyanthraquinone 81L, Onml, 8-dihydroxyanthraquinone 482.5HsNext, the state of film formation by each color development abrasion is shown below.

Color developer name Film-forming state α-naphthol ◎β-naphthol
O1,2-naphthalene diol
△1.3-naphthalene diol
01.4-Naphthalene diol 01.5-
Naphthalene diol △1.6-naphthalene diol Ql, 7-naphthalene diol
O2,3-naphthalene diol
△2.6-naphthalenediol O2,7-
Naphthalene diol O1,2-dihydroxyanthraquinone O1,4-dihydroxyanthraquinone O1,8-dihydroxyanthraquinone
◎◎: Uniform and very good ×: Poor film formation O: Good △: Slight unevenness and pinholes In this way, products with respective dominant wavelengths usually result in good film formation. A color filter could be formed.

This result was achieved by fully utilizing the property of TAA itself, which has good adhesion to glass surfaces, and by selecting and adding an appropriate color developer to it. We were able to obtain such excellent data.

Furthermore, the spectral characteristics when the coloring material formed in this manner was applied were also similar to those of conventional coloring materials.

The coloring material formed in this way is orange in the case of a naphthalene compound developer, and blue or red in the case of an anthraquinone compound developer, and is useful for molding various color filters. It can be of great use when

On the other hand, in the case of a coloring material produced by adding an anthraquinone compound to a TAA treatment liquid, there is a method in which it is appropriately coated or printed on the surface of a predetermined translucent plate material, and then developed by irradiating ultraviolet rays to form a color pattern. Since the anthraquinone compound itself has photosensitivity, it is possible to develop various patterns, which, together with good adhesion of coloring materials, improves accuracy in color filter pixel molding. This will greatly contribute to the

It goes without saying that the method for producing a coloring material for a color filter and the method for producing a color filter according to the present invention are not limited to the above-mentioned embodiments. kinds,
It is not limited to the ratio, etc., and any type and ratio may be used as long as it has good responsiveness and excellent color development.

(Effects of the Invention) As described above, according to the present invention, the acidic solution of the titanium (IV value) acetylacetonate complex (1; 2) and either the naphthalene compound or the anthraquinone compound are mixed in a predetermined ratio. By reacting with titanium (
By utilizing the good adhesion of the acetylacetonato complex (1:2) itself and making it an acidic solution, hydrolysis with water on the filter surface is suppressed as much as possible to prevent clouding, and Since the colorant is formed by reaction with either a naphthalene compound or an anthraquinone compound, it can be a non-polymer colorant, so it has similar color development and spectral properties compared to polymer colorants. It is possible to ensure strong adhesion.

In addition, the color filter, in which a color pattern is formed on the surface of a predetermined light-transmitting plate using the colorant formed in this way, has good adhesion to the colorant itself, so it cannot be used with conventional picture element forming methods. Even if such a method is used, pattern accuracy and positional accuracy can be greatly improved, and moreover, even if a picture element forming method, such as a printing method, can be used at a low cost, it can be formed with high precision.

Furthermore, at that time, in the case of a combination of an acidic solution of titanium (IV value) acetylacetonato complex (1:2) and an anthraquinone compound, a coloring material is appropriately applied to the surface of a predetermined transparent and transparent board material. It is coated or printed, and then developed by irradiating ultraviolet rays.The color pattern is photosensitive, so it is possible to develop various patterns, and it has good adhesion of coloring materials when forming color filter pixels. Together with this, this greatly contributes to improving accuracy.

As described above, according to the present invention, since it is a non-polymer coloring material and has strong adhesion, the coloring material can be produced in a variety of colors from orange to red to blue. In addition to being able to provide accurate color filters at low cost, the range of application to new color filters can be expanded, and various excellent effects can be achieved, such as making it possible to use them in a wide variety of areas.

Patent applicant Toin Co., Ltd.
Ceremony Company representative Patent attorney Masa Nakamura Migai (1 person)

Claims (1)

[Claims] 1. Titanium (IV value) acetylacetonate complex (1:2)
A method for producing a coloring material for a color filter, comprising reacting an acidic solution of the above with either a naphthalene compound or an anthraquinone compound at a predetermined ratio. 2. Titanium (IV value) acetylacetonate complex (1:2)
A color pattern is formed on the surface of a predetermined light-transmitting plate using a coloring material for color filters formed by reacting an acidic solution of 1 with either a naphthalene compound or an anthraquinone compound in a predetermined ratio. Featured color filter manufacturing method. 3. Titanium (IV value) acetylacetonato complex (1:2)
A coloring material for a color filter, which is formed by reacting an acidic solution of and an anthraquinone compound in a predetermined ratio, is appropriately coated or printed on the surface of a predetermined translucent plate material, and then developed by irradiating ultraviolet rays to form a color pattern. A color filter manufacturing method characterized by forming a color filter.