JPH10268128A - Light-shielding paint composition for color filter containing coupling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-shielding coating composition excellent in various properties required for a light-shielding thin film such as a color filter for LCD, particularly excellent in light resistance and moisture resistance, and to have a light-shielding thin film on a surface. Provided is a method for manufacturing a high-quality substrate. A light-shielding material and a polymer material are contained,
A light-shielding coating composition obtained by mixing one or more specific coupling agents is produced, and a substrate is produced using the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-shielding coating composition useful for forming a light-shielding thin film of a color filter used for a liquid crystal display device or an image pickup device.

[0002]

2. Description of the Related Art In a color filter used for a liquid crystal display device (LCD) or the like, a red filter formed on a transparent substrate is used to improve contrast and color purity or to prevent light leakage to a switching device or the like. It is known to provide a light-shielding thin film called a black matrix in the gap between each of the green and blue transparent colored fine patterns, and to provide a light-shielding thin film that blocks unnecessary light on a substrate disposed on a switching element. .

In recent years, LCDs have rapidly increased in size and definition,
With the increase in production volume, etc., demands for various characteristics, productivity, and the like of the light-shielding thin film have been further strengthened. For example, in addition to high light-shielding properties, flatness and smoothness of coating films, better adhesion to substrates and overcoats (protective films), and more recently, especially light resistance, heat resistance, and water resistance There is a strong demand for reliability such as moisture resistance, alkali resistance, acid resistance, solvent resistance, and liquid crystal resistance.

As materials for forming such a light-shielding thin film, metal-based and resin-based materials are mainly used.
A chromium or the like is used as the metal-based material, and a coating composition containing a polymer material such as a resin and a light-shielding material such as carbon black is used as the resin-based material.

[0005]

A coating composition for providing a thin film having excellent properties such as light resistance and moisture resistance required for a light-shielding thin film of a color filter used in a liquid crystal display device or the like. Sufficient ones have not been found.

[0006]

Means for Solving the Problems The present inventors have found that the above problems can be solved by adding a coupling agent to a coating composition containing a light-shielding material, and have completed the present invention. Was. That is, the present invention provides (1) a light-shielding coating composition for a color filter, wherein (1) a light-shielding coating composition for a color filter, wherein one or a mixture of two or more coupling agents is blended. A method for producing a substrate having a light-shielding thin film for a color filter, comprising forming a light-shielding thin film on a substrate by using the coating composition of (1).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The coupling agent used in the present invention has a general structure of R—Si (OR ′) ₃ ｛R, an organic functional group such as vinyl or amino, and R ′, a hydrolysis such as halide, acyloxy, or alkoxy group. Silane-based coupling agents represented by the functional group 、, for example, vinyltrichlorosilane, γ
-Aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane and the like. The general structure is represented by RO-Ti-OR '(R is an organic functional group such as an alkyl ester, carboxyphosphate, pyrophosphate phosphite sulfonyl, and R' is a hydrolyzable group such as an alkoxy group). And titanium-based coupling agents such as isopropyl triisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, isopropyl tridodecylbenzenesulfonyl titanate and the like. Aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate, ethyl acetoacetate aluminum diisopropylate, and aluminum tris (acetylacetonate). And a zircoaluminate coupling agent, for example, tetrapropyl zircoaluminate, etc., can be mentioned, and one or a mixture of two or more thereof can be used.

The amount of the coupling agent used in the present invention varies depending on the type and characteristics of the coupling agent. However, in view of the storage stability of the light-shielding coating composition and various characteristics of the light-shielding thin film formed by the composition, Usually, it is desirable to appropriately select from the range of 0.1 to 30.0% by weight based on the total solid content. When the amount is less than 0.1%, the adhesion to the glass substrate is not sufficient when a deterioration test is performed under light irradiation or in a high humidity atmosphere. When the amount exceeds 30%, the storage stability of the coating material is deteriorated, which is preferable. Absent.

The light-shielding material used in the present invention includes metal oxides such as carbon black, titanium black and black iron oxide, metal sulfides such as bismuth sulfide, organic pigments such as periogen black, cyanine blue, and dioxazine violet. And the like, and one or a mixture of two or more of these can be used.

The polymer material used in the coating composition of the present invention includes a photosensitive coating, an alkali or solvent-soluble coating,
Known photo-curable resins each of which has been conventionally used, such as an electrodeposition paint or a printing ink, can be used without any particular limitation.

The weight ratio of the light-shielding material to the photocurable resin used as the polymer material in terms of solid content is preferably from 10 to 70:90 to 30 in view of various characteristics of the formed light-shielding thin film.

Further, the coating composition of the present invention may contain a commonly used photopolymerization initiator according to the conditions of irradiation with ultraviolet rays. Benzoins such as benzoin, benzoin methyl ether, and the like,
Acetophenone, acetophenones such as 2,2-dimethkin-2-phenylacetophenone, anthraquinones such as 2-ethylanthraquinone, thioxanthones such as 2,4-dimethylthioxanthone, and ketals such as acetophenone dimethyl ketal are exemplified. The amount used is appropriately 0.1 to 10% by weight based on the solid content of the photocurable resin and the light-shielding material used as the polymer material.

The coating composition of the present invention may further contain, if necessary, a photoreactive diluent, an organic solvent, a polymerization inhibitor, a dispersing aid, a spreading agent, a thickening (low) viscosity agent, and other fillers. Agents and the like may be used as appropriate.

The coating composition of the present invention thus obtained is particularly useful for producing a substrate having a light-shielding thin film called a black matrix on the surface. Such a light-shielding thin film can be formed by a known method on a substrate on which a transparent colored fine pattern such as red, green and blue may be formed. That is, the light-shielding thin film may be formed in the gap between the transparent colored fine patterns after or before the formation of the transparent colored fine patterns, or may be formed on another substrate independently of the transparent colored fine patterns. it can.

For example, a transparent colored fine pattern is formed on a transparent substrate such as glass by a known method such as a printing method, a photolithography method, and an electrodeposition method.
By using the coating composition of the present invention to form a light-shielding thin film by a known method, a substrate having a light-shielding thin film in a gap between transparent colored fine patterns can be manufactured.

Specifically, for example, Japanese Patent Application Laid-Open No. 62-247
No. 331, a desired transparent colored fine pattern is formed on a transparent substrate by an electrodeposition method, and then the coating composition of the present invention is coated on the substrate so as to cover the formed transparent colored fine pattern. A desired substrate can be obtained by a method well-known as a so-called back exposure method, in which application is performed on the entire surface of the substrate, and then exposure and development are performed from the back surface of the substrate.

Alternatively, according to the method described in Japanese Patent Application Laid-Open No. 7-35920, a desired light-shielding thin film in the form of a window frame is first formed, and then a transparent colored fine pattern of the window frame is formed. A substrate can be obtained.

Conventionally, the light-shielding thin film obtained by such a method has been required to have a high quality at present, and when a reliability test of light resistance is carried out, a problem of 240 hours in a sunshine weather test of JIS B 7752 is obtained. However, if the time is longer than that, there is a problem that the light-shielding thin film is peeled off at the interface with the glass. For example, LCDs mounted on automobiles and LCDs used outdoors are expected to have higher light resistance in the future. In contrast, the coating composition of the present invention is considered to be sufficiently useful because it has a performance of 480 hours or more in the above test.

[0019]

The present invention will be described in more detail with reference to the following examples. In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified.

Example 1 1) 5 parts of acetoalkoxyaluminum diisopropylate 2) 2 parts of γ-aminopropyltriethoxysilane 3) 100 parts of propylene glycol monomethyl ether 4) 40 parts of carbon black 5) 60 parts of propylene oxide-modified bisphenol A Diepoxy diacrylate adduct 6) Irgacure 907 1 part (photoinitiator, Ciba-Geigy)

The mixture of (1), (2), (3), (4) and (5) was dispersed in a glass bead mill for 5 hours, and the dispersion was further dispersed in a roll mill. I got something.

The obtained coating composition was applied to the entire surface of a glass substrate by screen printing so as to cover a transparent colored fine pattern such as red, green and blue formed by a known method. After pre-drying at 90 ° C for 10 minutes, U
Ultraviolet rays were irradiated from the back side using VC-5039 (made by Ushio Inc.). The exposure conditions were 80 W / cm, height 240 mm, and conveyor speed 1200 mm / min. After exposure, it was immersed in butyl cellosolve at room temperature for 30 minutes. Next, the substrate was washed with deionized water, and after confirming that the cleaning water was clear, it was immersed and rocked in isopropanol,
It was baked and dried at 00 ° C for 60 minutes.

As described above, on a glass substrate, a film having a thickness of 1 μm, a predetermined stable shape, a high light-shielding property, good adhesion to glass, and various characteristics required for a color filter can be obtained. Thus, a glass substrate on which an excellent light-shielding thin film was formed was obtained. The substrate was subjected to an accelerated weathering test for 480 hours using a sunshine weather meter, but no deterioration was observed in the adhesion between the light-shielding thin film and the glass. Further, even after the light-shielding coating composition obtained above was stored in a cool and dark place for one month, no deterioration was observed and the storage stability was excellent.

Example 2 5 parts of tetra (2.2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate was added to 100 parts of a commercially available light-shielding paint, CFPR-BK-710 (manufactured by Tokyo Ohka Co., Ltd.). It was added and mixed uniformly to obtain a light-shielding coating composition.

The obtained coating composition was applied to the entire surface of a glass substrate by a spin coater. After preliminary drying at 90 ° C. for 10 minutes, ultraviolet irradiation was performed using a mask such that the exposed portion had a stripe width of 20 μm and the light-shielded portion had a stripe width of 80 μm. UVC-5039 (Ushio Inc.) was used as the apparatus, and the irradiation exposure conditions were 80 W / cm.
The height was 240 mm and the conveyor speed was 1200 mm / min. After the exposure, the film was immersed in 3% sodium carbonate at room temperature for 30 minutes. Next, the substrate was washed with deionized water, and after confirming that the cleaning water was clear, it was baked and dried at 200 ° C. for 60 minutes.

As described above, on a glass substrate, a film having a thickness of 1 μm, a predetermined stable shape, a high light-shielding property, good adhesion to glass, and various characteristics required for a color filter are obtained. Thus, a glass substrate on which an excellent light-shielding thin film was formed was obtained. The substrate was subjected to an accelerated weathering test for 480 hours using a sunshine weather meter, but no deterioration was observed in the adhesion between the light-shielding thin film and the glass. Further, even after the light-shielding coating composition obtained above was stored in a cool and dark place for one month, no deterioration was observed and the storage stability was excellent.

Comparative Example 1 A glass substrate on which a similar light-shielding thin film was formed was obtained using the coating composition containing no coupling agent in Example 1. The obtained substrate had no problem in the accelerated weathering test for 240 hours, but peeled off the thin film in 260 hours.

[0028]

According to the present invention, a light-shielding thin film having a fine and predetermined shape, which has high light-shielding properties and is excellent in storage stability such as light resistance and moisture resistance, is formed irrespective of its forming method. Therefore, a light-shielding coating composition which is particularly useful for forming a light-shielding thin film of a color filter for an LCD is provided industrially advantageously.

Claims (3)

[Claims] 1. A light-shielding coating composition for a color filter, which comprises one or a mixture of two or more coupling agents. 2. The content of one or a mixture of two or more coupling agents is 0.1 to 30.0% based on the total solid content.
The composition of claim 1, which is in weight percent. 3. A method for producing a substrate having a light-shielding thin film for a color filter, comprising forming a light-shielding thin film on the substrate using the composition according to claim 1.