JP3455974B2 - Manufacturing method of black matrix substrate - 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 for manufacturing a black matrix substrate, and more particularly to a method for manufacturing a black matrix substrate having high dimensional accuracy and excellent light-shielding property.

[0002]

2. Description of the Related Art In recent years, monochrome or color liquid crystal displays have been attracting attention as flat displays. Liquid crystal displays include an active matrix system and a simple matrix system for controlling three primary colors, and a color filter is used in each system. In the color liquid crystal display, the constituent pixel portions have three primary colors (R, G, B), and the transmission of each light of the three primary colors is controlled by electrical switching of the liquid crystal to perform color display.

This color filter is constructed by forming each colored layer, a protective layer and a transparent electrode layer on a transparent substrate.
And in order to increase the coloring effect and display contrast,
A light-shielding layer (black matrix) is formed at the boundary between the R, G, and B pixels of the colored layer. Further, in an active matrix type liquid crystal display, since a thin film transistor (TFT) is used as a switching element, it is necessary to suppress light leak current. Therefore, a higher light blocking property is required for the light blocking layer (black matrix). Such a light shielding layer (black matrix) is required not only for color liquid crystal displays but also for monochrome liquid crystal displays for the same reason.

Conventionally, as the light-shielding layer (black matrix), a chromium thin film is photo-etched to form a relief, a hydrophilic resin relief is dyed, a relief formed using a photosensitive solution in which a black pigment is dispersed,
There are those formed by electrodeposition of black electrodeposition paint, those formed by printing, and the like.

However, although the chrome thin film is photo-etched and relief-formed, the dimensional accuracy is high, but the vacuum film-forming process such as vapor deposition or sputtering is required and the manufacturing process is complicated. The cost is high, and it is necessary to suppress the reflectance of chrome in order to increase the display contrast under strong external light. Therefore, it is necessary to perform sputtering of low reflection chrome, which is more costly to manufacture. Further, the method of using a photosensitive resist in which the above black dye or pigment is dispersed, the manufacturing cost is low, but the photoprocess tends to be insufficient because the photosensitive resist is black, and it is difficult to obtain sufficient light shielding properties. However, there is a problem that a high quality black matrix cannot be obtained. Further, the black matrix formation by the above-mentioned printing method can reduce the manufacturing cost, but has a problem that the dimensional accuracy is low.

[0006]

In order to solve the above-mentioned problems, the electroless plating catalyst is applied to the relief formed by exposing and developing a photosensitive resist layer containing a hydrophilic resin in a predetermined pattern. Containing a metal compound to be
After heat treatment, a method of depositing metal particles in the relief by electroless plating to form a light-shielding layer, or a photosensitive resist layer containing a hydrophilic resin and a metal compound serving as a catalyst for electroless plating There is a method in which after heat-treating a relief formed by exposing and developing with a predetermined pattern, metal particles are deposited in the relief by electroless plating to form a light-shielding layer (JP-A-5-303090).
issue). The light-shielding layer obtained by this method has high optical density and low reflectance and good dimensional accuracy,
Manufacturing cost can be reduced because no vacuum process is required.

However, in the actual production of a black matrix substrate, in order to prevent damage to the photomask and shorten the exposure processing time, the conventional contact exposure is shifting to proximity exposure. Generally, the proximity exposure tends to have a lower resolution than the contact exposure, and the above-mentioned JP-A-5-30309.
Even in the method disclosed in No. 0, there is a problem that sufficient resolution cannot be obtained when the proximity exposure is adopted. The reason for this is that since it is necessary to deposit a metal by electroless plating in the relief, a photosensitive resist (photosensitive resin) containing a hydrophilic resin is given a swelling property with respect to water. Due to the swelling property, the relief may be thickened, deformed, and edge-shaped sagging may occur during the developing process.

The present invention has been made in view of the above-mentioned circumstances, and a black matrix substrate having sufficient resolution and high optical density can be manufactured at low cost even when proximity exposure is adopted. It is an object of the present invention to provide a manufacturing method that can be performed.

[0009]

In order to achieve such an object, the present invention exposes and develops a photosensitive resin layer formed on a transparent substrate through a photomask having a black matrix pattern. A relief is formed on the transparent substrate, the transparent substrate is brought into contact with an aqueous solution of a metal compound serving as a catalyst for electroless plating to contain the metal compound in the relief to form a catalyst-containing relief, and then the catalyst-containing relief. In the method for producing a black matrix substrate, wherein the light-shielding layer having a pattern for black matrix is formed by contacting the above with an electroless plating solution, the photosensitive resin layer is an α-substituted acrylamide or an N-mono substituted acrylamide. , An N, N-disubstituted acrylamide and an N-monosubstituted methacrylamide. A water-soluble photosensitive resin composition containing a water-soluble resin having a polymer using at least one monomer selected from the group of amide-based monomers and a cross-linking agent having a water-soluble azide compound. It has a different structure.

Further, according to the present invention, a photosensitive resin layer containing a metal compound serving as a catalyst for electroless plating formed on a transparent substrate is exposed and developed through a photomask having a black matrix pattern, and the transparent layer is formed. In the method for producing a black matrix substrate, the catalyst-containing relief is formed on a substrate, and then the catalyst-containing relief is brought into contact with an electroless plating solution to form a light-shielding layer having a black matrix pattern. Is an α-substituted form of acrylamide, N of acrylamide
At least one selected from the group of acrylamide monomers consisting of a mono-substituted product, an N, N-di-substituted product of acrylamide and an N-mono-substituted product of methacrylamide.
The water-soluble photosensitive resin composition containing a water-soluble resin having a polymer using one kind of monomer and a crosslinking agent having a water-soluble azide compound is used.

[0011]

[Function] The relief for the black matrix formed on the transparent substrate is electroless plated to deposit a metal to form a light-shielding layer. The photosensitive resin layer for forming this relief by exposure and development is Since it is formed using a water-soluble photosensitive resin composition containing a water-soluble resin having a polymer using at least one kind of the above-mentioned acrylamide-based monomer and a cross-linking agent having a water-soluble azide compound. , Relief thickening, deformation, and edge shape sagging do not occur in the development process, and metal particles are deposited almost uniformly on the entire relief, so even if proximity exposure is adopted, resolution and optical density It is possible to obtain a black matrix substrate having high dimensional accuracy and high reflectivity and low reflectance.

[0012]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a perspective view showing an example of an active matrix type liquid crystal display (LCD) using a black matrix substrate manufactured according to the present invention, and FIG. 2 is a schematic sectional view of the same. 1 and 2, the LCD 1 has a color filter 10 and a transparent glass substrate 20 which are opposed to each other with a sealing material 30 in between, and a thickness of about 5 to 1 made of twisted nematic (TN) liquid crystal between them.
A liquid crystal layer 40 having a thickness of about 0 μm is formed, and polarizing plates 50 and 5 are provided outside the color filter 10 and the transparent glass substrate 20.
1 is provided and configured.

FIG. 3 is an enlarged partial sectional view of the color filter 10. In FIG. 3, the color filter 10 includes a black matrix substrate 12 in which a light shielding layer (black matrix) 14 is formed on a transparent substrate 13, a coloring layer 16 formed between the black matrices 14 of the black matrix substrate 12, and the black layer. Matrix 14
And a protective layer 18 and a transparent electrode 19 provided so as to cover the colored layer 16. The color filter 10 is arranged such that the transparent electrode 19 is located on the liquid crystal layer 40 side. The colored layer 16 is composed of a red pattern 16R, a green pattern 16G, and a blue pattern 16B, and the array of each colored pattern is a mosaic array as shown in FIG. The arrangement of the coloring pattern is not limited to this, and may be a triangular arrangement, a stripe arrangement, or the like.

Display electrodes 22 are provided on the transparent glass substrate 20 so as to correspond to the colored patterns 16R, 16G, 16B, and each display electrode 22 has a thin film transistor (TFT) 24. Further, a scanning line (gate electrode busbar) 26a and a data line 26b are arranged between the respective display electrodes 22 so as to correspond to the black matrix 14.

In the LCD 1 as described above, each of the colored patterns 16R, 16G and 16B constitutes a pixel, and the display electrode corresponding to each pixel is turned on and off in a state in which the illumination light is irradiated from the polarizing plate 51 side, whereby the liquid crystal is formed. The layer 40 operates as a shutter, and light is transmitted through each pixel of the colored patterns 16R, 16G, and 16B to perform color display.

The transparent substrate 13 of the black matrix substrate 12 constituting the color filter 10 is a rigid material such as quartz glass, low expansion glass or soda lime glass, a transparent resin film, an optical resin plate or the like. It is possible to use a flexible material having such flexibility. Among them, Corning 7059 glass is a material with a small coefficient of thermal expansion, has excellent dimensional stability and workability in high-temperature heat treatment, and is a non-alkali glass that does not contain an alkali component in the glass. It is suitable for a matrix type LCD color filter.

An example of manufacturing the black matrix substrate 12 according to the present invention will be described with reference to FIG. First, the water-soluble photosensitive resin composition is applied on the transparent substrate 13 to have a thickness of 0.1 to 5.0 μm, preferably 0.1 to 2.0 μm.
The photosensitive resin layer 3 having a thickness of about m is formed (FIG. 4A). When the thickness of the photosensitive resin layer 3 is less than 0.1 μm, the deposition of metal particles in electroless plating described below becomes insufficient,
A light-shielding layer having a sufficient optical density cannot be obtained, and a thickness of more than 5.0 μm lowers the resolution, which is not preferable. From the viewpoint of surface irregularities, the thickness of the photosensitive resin layer 3 is preferably 2.0 μm or less. Next, the photosensitive resin layer 3 is proximity-exposed through the photomask 9 for the black matrix (FIG. 4 (B)). The exposure may be contact exposure. Then, the exposed photosensitive resin layer 3 is developed to form a relief 4 having a pattern for a black matrix (FIG. 4C). next,
The transparent substrate 13 is dipped in an aqueous solution of a metal compound serving as a catalyst for electroless plating, washed with water, dried, and then heat treated (10
The catalyst-containing relief 5 is formed by applying 0 to 200 ° C. for 5 to 30 minutes (FIG. 4 (D)). Then, the catalyst-containing relief 5 on the transparent substrate 13 is brought into contact with an electroless plating solution to form a black matrix 14 as a light shielding layer (FIG. 4 (E)).

Another example of manufacturing the black matrix substrate 12 according to the present invention will be described with reference to FIG. First, a water-soluble photosensitive resin composition containing an aqueous solution of a metal compound serving as a catalyst for electroless plating is applied on the transparent substrate 13 to have a thickness of 0.1 to 5.0 μm, preferably 0.1 to 2.0.
A photosensitive resin layer 7 having a thickness of about μm is formed (FIG. 5A).
Next, the photosensitive resin layer 7 is proximity-exposed through the photomask 9 for the black matrix (FIG. 5).
(B)). The exposure may be contact exposure. Then, after the exposed photosensitive resin layer 7 is developed and dried, heat treatment (100 to 200 ° C., 5 to 30 minutes) is performed to form a catalyst-containing relief 8 having a pattern for a black matrix (FIG. 5). (C)). Next, this transparent substrate 1
The black matrix 14 is formed by contacting the catalyst-containing relief 8 on 3 with the electroless plating solution to form a light-shielding layer (FIG. 5 (D)).

In the present invention, the water-soluble photosensitive resin composition used for forming the photosensitive resin layer contains a water-soluble resin and a crosslinking agent.

The water-soluble resin constituting the above water-soluble photosensitive resin composition is an α-substituted acrylamide, an N-monosubstituted acrylamide, an N, N-disubstituted acrylamide and an N-substituted methacrylamide. It has a polymer using at least one kind of monomer selected from the group of acrylamide monomers consisting of mono-substituted products.

Examples of α-substituted acrylamides usable in the above polymers include methacrylamide (= α · methylacrylamide) and α · phenylacrylamide. Further, N-monosubstituted acrylamides include N-isopropylacrylamide and N-isopropylacrylamide.
Examples thereof include -t-octyl acrylamide, N-methylol acrylamide, N, N'-methylene bis (acrylamide), N-diacetone acrylamide, N- (n-butoxymethyl) acrylamide, N, N-dimethylaminopropyl acrylamide. Examples of N, N-disubstituted acrylamides include N, N-dimethylacrylamide, N, N-diethylacrylamide and acrylmorpholine. Furthermore, examples of the N-mono-substituted methacrylamide include N-methyl methacrylamide and the like.

The water-soluble resin constituting the water-soluble photosensitive resin composition used in the present invention is a polymer using at least one kind of the above-mentioned acrylamide type monomer, and is a copolymer or a homopolymer. Either may be used. When the water-soluble resin is a copolymer, the monomer may be a combination of two or more of the above-mentioned acrylamide-based monomers, or a combination of the above-mentioned acrylamide-based monomers and other monomers. Examples of the other monomer that can be copolymerized with the acrylamide-based monomer include water-soluble monomers such as acrylonitrile, acrylamide and acrylic acid, and water-insoluble monomers such as styrene, vinyl chloride and methyl methacrylate. The rate at which these monomers to be copolymerized are introduced into the copolymer depends largely on the combination of the monomers, but if the rate of introduction of other monomers becomes too high, crosslinking due to the acrylamide monomer will occur. It is desirable that the amount of the other monomer with respect to the acrylamide monomer is 60% by weight or less, and preferably 20% by weight or less, since the property of being easily adhered to the substrate is deteriorated. Further, the copolymerization of the above-mentioned acrylamide-based monomer and other monomer,
It can be carried out by a known method such as radical polymerization.

When the water-soluble resin is a homopolymer, the acrylamide-based monomers which are preferably used in terms of water-solubility are methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N, N. -Although limited to dimethylaminopropyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, etc., acrylamide-based properties such as easy crosslinking, high water absorption, good adhesion, and hardness Such characteristics are preferable because they are more clearly imparted to the water-soluble resin.

As the water-soluble resin constituting the water-soluble photosensitive resin composition used in the present invention, a mixture of the above-mentioned copolymer or homopolymer and another water-soluble polymer may be used. it can. Examples of other water-soluble polymers include gelatin, casein, glue, gum arabic, shellac, natural polymers such as ovalbumin, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and anhydrous. Mention may be made of synthetic polymers such as maleic acid copolymers, or copolymers thereof. In this case, the proportion of the other water-soluble polymer in the water-soluble resin is desirably 60% by weight or less, preferably 20% by weight or less. This ratio is 60% by weight
If it exceeds, the properties of the other water-soluble resin will be more dominant than the properties of the water-soluble resin containing the acrylamide monomer, and the properties of the water-soluble resin containing the acrylamide monomer will not be sufficiently exhibited, which is not preferable.

As the crosslinking agent constituting the water-soluble photosensitive resin composition used in the present invention, 4,4'-diazidostilbene-2,2'-disulfonic acid and its disodium salt, dipotassium salt, or Examples thereof include water-soluble azide compounds such as organic amine salts thereof (organic amines include 3-hydroxypropylamine, ethoxyethylamine, diethanolamine, triethylamine, tetramethylammonium, tetraethylammonium, etc.).

The water-soluble photosensitive resin composition used in the present invention is obtained by dissolving the above water-soluble resin and crosslinking agent in water. Then, the total amount of the water-soluble resin solid content and the cross-linking agent solid content in the water-soluble photosensitive resin composition can be determined according to the coating device used. For example, when a spin coater is used, the total amount of water-soluble resin solids and crosslinking agent solids is preferably about 1 to 10% by weight of the water-soluble photosensitive resin composition. If this ratio is less than 1% by weight, a sufficient coating film thickness cannot be obtained because the solid content ratio is too low. On the other hand, if it exceeds 10% by weight, the viscosity of the water-soluble photosensitive resin composition is too high, and the suitability for coating by the spin coating method is deteriorated, and a uniform film thickness cannot be obtained, which is not preferable. The ratio of the cross-linking agent to the water-soluble resin is preferably about 5-20% by weight. If this ratio is less than 5% by weight, the sensitivity of the water-soluble photosensitive resin composition will be insufficient, and if it exceeds 20% by weight, film peeling will occur during development, which is not preferable. It is presumed that this film peeling occurs because the adhesion between the substrate and the water-soluble photosensitive resin composition is reduced.

Further, the water-soluble photosensitive resin composition used in the present invention contains additives such as a surfactant and a silane coupling agent, if necessary, in addition to the above-mentioned water-soluble resin and crosslinking agent. You may let me.

Since the photosensitive resin layer is formed by using the water-soluble photosensitive resin composition as described above, the relief is not broken during the developing process, and the catalyst-containing relief 5, as described above, is used. When 8 contacts the electroless plating solution, the electroless plating solution easily penetrates into the catalyst-containing relief, and the metal particles are uniformly deposited in the catalyst-containing relief. Therefore, the formed black matrix 14 has a high resolution, a sufficient optical density, and a low reflectance, so that the problem of reflection by the metal layer in the conventional chromium thin film formation can be solved, and the proximity exposure is used. It becomes possible to manufacture a high quality black matrix substrate.

The metal compound used as a catalyst for electroless plating used in the present invention includes chlorides such as palladium, gold, silver, platinum and copper, water-soluble salts such as nitrates, and complex compounds, which are commercially available as an aqueous solution. The existing activator solution for electroless plating can be used as it is. When such a metal compound is contained in the water-soluble photosensitive resin composition as described above, 0.00001 to 0.
It is preferably contained in an amount of about 001% by weight.

The electroless plating solution is, for example, a reducing agent such as hypophosphorous acid, sodium hypophosphite, sodium borohydride, N-dimethylamineborane, borazine derivative, hydrazine and formalin, and nickel, cobalt,
Iron, copper, water-soluble reducible heavy metal salts such as chromium, plating rate, caustic soda for improving the reduction efficiency and the like, basic compounds such as ammonium hydroxide, inorganic acids, pH adjusters such as organic acids, Buffer agents typified by alkali salts of oxycarboxylic acids such as sodium citrate and sodium acetate, boric acid, carbonic acid, organic acids, and inorganic acids, complexing agents for the purpose of stabilizing heavy metal ions, and accelerators An electroless plating solution containing a stabilizer, a surfactant, and the like is used.

Two or more electroless plating solutions may be used in combination. For example, first, an electroless plating solution containing a boron-based reducing agent such as sodium borohydride that is easy to form a nucleus (for example, a nucleus of palladium when palladium is used as a metal compound serving as a catalyst for electroless plating) is used. ,
Next, an electroless plating solution containing a hypophosphorous acid-based reducing agent having a high metal deposition rate can be used.

In any of the above-described methods for manufacturing a black matrix substrate, the wavelength 545 of the obtained light shielding layer is obtained.
The reflectance in nm is 30% at the maximum, usually 5% or less, which is extremely lower than the reflectance (50 to 80%) of the conventional light shielding layer made of a chromium thin film, and good display quality can be obtained. .

The light-shielding layer has a maximum particle size of the metal particles dispersed therein of 0.05 μm, usually 0.01 to
It is 0.02 μm, and a uniform film having no unevenness is formed.

In any of the above-mentioned methods for manufacturing a black matrix substrate, a light-shielding layer having an optical density of 3.0 or more can be obtained by changing the plating time. From the viewpoint of improving the optical density, an optical density of 2.0 or more is preferable. Optical density 2.
When it is less than 0, it does not sufficiently function as a light-shielding layer and cannot be put to practical use as a black matrix substrate.

Further, the film thickness of the light-shielding layer can be freely set by changing the coating film thickness of the water-soluble photosensitive resin composition. And from the viewpoint of optical density, the thickness of the light shielding layer is in the range of 0.1 to 5.0 μm, preferably 0.1 to 2.0 μm.

Black matrix substrate 1 as described above
The formation of the colored layer 16 including the red pattern 16R, the green pattern 16G, and the blue pattern 16B between the two black matrices 14 can be performed by various known methods such as a dyeing method, a dispersion method, a printing method, and an electrodeposition method. it can.

A protective layer 18 provided so as to cover the black matrix 14 and the colored layer 16 of the color filter 10.
Is for smoothing the surface of the color filter 10, improving reliability,
Also, the purpose is to prevent contamination of the liquid crystal layer 40 and the like, and can be formed using a transparent resin such as an acrylic resin, an epoxy resin, a polyimide resin, or a transparent inorganic compound such as silicon dioxide. . The thickness of the protective layer is preferably about 0.5 to 50 μm.

As the transparent common electrode 19, for example, an indium tin oxide (ITO) film can be used. IT
The O film can be formed by a known method such as a vapor deposition method and a sputtering method, and the thickness is preferably about 200 to 2000 Å.

Next, the present invention will be described in more detail by showing specific examples. Example 1 First, as a water-soluble resin, a copolymer of one kind of acrylamide-based monomer (N-mono-substituted acrylamide) and another monomer was used. Resin composition 1 was prepared. (Composition of water-soluble photosensitive resin composition 1) N-diacetone acrylamide / acrylamide copolymer 2.7 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.3 parts by weight of water ... 97 parts by weight of silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.03 parts by weight Next, as a transparent substrate, 7059 glass manufactured by Corning Co. (thickness = 1) 0.1 mm) and the above water-soluble photosensitive resin composition 1 is applied onto a transparent substrate by spin coating (rotation speed = 1000 rpm), and then prebaked at 70 ° C. for 5 minutes to expose it. Resin layer (thickness = 0.6μ
m) was formed.

Then, with a proximity exposure machine equipped with a 2 kW ultra-high pressure mercury lamp, the above-mentioned photosensitive resin layer was exposed with an exposure dose of 10 mJ / cm ² through a photomask for a black matrix having a line & space pattern. went. The proximity gap amount is 100μ
set to m. Then, after performing spray development for 45 seconds using water at room temperature, post-baking was performed at 100 ° C. for 5 minutes to form a relief for a black matrix.

Next, this transparent substrate was dipped in a 100 ppm palladium chloride aqueous solution (Red Schumer made by Kanigen Japan Co., Ltd.) for 30 seconds, washed with water, and dried to obtain the above relief as a catalyst-containing relief.

The above transparent substrate contains a boron-based reducing agent 2
Nickel plating solution at 3 ℃ (BEL ・ 801 made by Uemura Kogyo)
After immersing in water for 4 minutes, washing with water and drying to form a light-shielding layer (black matrix), curing was performed at 200 ° C. for 30 minutes to obtain a black matrix substrate (Sample 1). Examples 2 to 4 Black matrix substrates (Samples 2 to 4) were obtained in the same manner as in Example 1 except that the following water-soluble photosensitive compositions 2 to 4 were used as the water-soluble photosensitive resin compositions. It was Each of the water-soluble photosensitive compositions 2 to 4 used as a water-soluble resin a copolymer of one kind of acrylamide-based monomer (N-mono-substituted acrylamide) and another monomer. , A homopolymer of one kind of acrylamide-based monomers (N, N-substituted acrylamide), and two kinds of acrylamide-based monomers (N, N-substituted acrylamide) And N-mono-substituted product) were used. (Composition of water-soluble photosensitive resin composition 2) N-diacetone acrylamide / polyvinyl alcohol copolymer 4.05 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.45 parts by weight Water ... 95.5 parts by weight Silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0.045 parts by weight (composition of water-soluble photosensitive resin composition 3) N, N-dimethyl acrylamide polymer: 4.5 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt: 0.5 parts by weight water: 95 parts by weight Surfactant (Nippon Oil and Fats Co., Ltd. LT-221) 0.2 parts by weight Silane coupling agent (Shin-Etsu Chemical Co., Ltd. KBM-603) 0.25 parts by weight (water-soluble photosensitive resin composition 4 Composition) ・ N, N-dimethyl ac Lamide / N-diacetone acrylamide copolymer 4.05 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt 0.45 parts by weight water 95.5 parts by weight Silane coupling agent (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.045 parts by weight Example 5 First, as a water-soluble resin, one kind of acrylamide monomer (N, N-substitution of acrylamide) was used. A water-soluble photosensitive resin composition 5 (including a metal compound serving as a catalyst for electroless plating) having the following composition was prepared using the homopolymer of (body). (Composition of water-soluble photosensitive resin composition 5) N, N-dimethylacrylamide polymer ... 4.5 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 5 parts by weight 2% dilute palladium chloride solution (hydrochloric acid concentration 6.3%) ... 2.5 parts by weight Water ... 92.5 parts by weight Surfactant (LT-221 manufactured by NOF Corporation) ... 2 parts by weight Silane coupling agent (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.25 parts by weight Next, under the same conditions as in Example 1, a photosensitive resin was formed on Corning 7059 glass as a transparent substrate. Layer (thickness = 0.6μ
m) was formed. Further, the photosensitive resin layer was exposed, spray-developed and post-baked under the same conditions as in Example 1 to form a catalyst-containing relief for the black matrix.

The catalyst-containing relief was subjected to electroless plating and curing under the same conditions as in Example 1 to obtain a black matrix substrate (Sample 5). Examples 6 to 7 Black matrix substrates (Samples 6 to 7) were obtained in the same manner as in Example 1 except that the following water-soluble photosensitive compositions 6 to 7 were used as the water-soluble photosensitive resin compositions. It was The water-soluble photosensitive compositions 6 to 7 use, as the water-soluble resin, a homopolymer of one kind of acrylamide monomers (N, N-dimethylacrylamide polymer) and use a water-soluble resin and a crosslinking agent. The ratio of the crosslinking agent to the total amount was changed to 20% by weight and 5% by weight, respectively. (Composition of water-soluble photosensitive resin composition 6) N, N-dimethylacrylamide polymer 4 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt 1 part by weight Water: 95 parts by weight ・ Surfactant (LT-221 manufactured by NOF CORPORATION): 0.2 parts by weight ・ Silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.): 0.25 parts by weight ( Composition of water-soluble photosensitive resin composition 7) N, N-dimethylacrylamide polymer ... 4.75 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.25 Parts by weight: Water: 95 parts by weight: Surfactant (LT-221 manufactured by NOF CORPORATION): 0.2 parts by weight: Silane coupling agent: KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd .: 0.25 and parts example 8 water-soluble photosensitive resin composition Other using a water-soluble photosensitive composition 8 The following was obtained black matrix substrate (sample 8) in the same manner as in Example 1. The water-soluble photosensitive composition 8 is a mixture of a homopolymer of one kind of acrylamide monomers (N, N-dimethylacrylamide polymer) and a homopolymer of another monomer as the water-soluble resin. Used. (Composition of water-soluble photosensitive resin composition 8) N, N-dimethyl acrylamide copolymer 2.5 parts by weight Polyvinylpyrrolidone 2 parts by weight 4,4'-diazidostilbene-2,2'- Disulfonic acid disodium salt: 0.5 parts by weight, water: 95 parts by weight, surfactant (LT-221 manufactured by NOF Corporation), 0.2 parts by weight, silane coupling agent (Shin-Etsu Chemical Co., Ltd.) KBM-603) 0.25 parts by weight Comparative Examples 1 to 3 The same as in Example 1 except that the following water-soluble photosensitive compositions I to III were used as the water-soluble photosensitive resin compositions. Black matrix substrates (Comparative Samples 1 to 3) were obtained. (Water-soluble photosensitive composition I) -Polyvinylpyrrolidone ... 4.05 parts by weight-4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.45 parts by weight-Water ... 95.5 Parts by weight Silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.045 parts by weight (water-soluble photosensitive composition II) Polyvinylpyrrolidone / polyvinyl alcohol mixture 4.05 parts by weight 4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.45 parts by weight water ... 95.5 parts by weight silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) ... 0 0.045 parts by weight (water-soluble photosensitive composition III) casein 9.0 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt 1.0 part by weight water 90.0 parts by weight Comparative Examples 4 to 5 Black matrix substrates (Comparative Samples 4 to 5) were prepared in the same manner as in Example 1 except that the following water-soluble photosensitive compositions IV to V were used as the water-soluble photosensitive resin compositions. Obtained. The water-soluble photosensitive compositions IV to V use a homopolymer of one kind of acrylamide monomers (N, N-dimethylacrylamide polymer) as a water-soluble resin,
The ratio of the cross-linking agent to the total amount of the water-soluble resin and the cross-linking agent,
It was changed to 25% by weight and 3% by weight, respectively. (Water-soluble photosensitive composition IV) N, N-dimethylacrylamide polymer ... 3.75 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 1.25 parts by weight Water: 95 parts by weight Surfactant (LT-221 manufactured by NOF Corporation): 0.2 parts by weight Silane coupling agent: KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd .: 0.25 parts by weight (Water-soluble photosensitive composition V) N, N-dimethylacrylamide polymer ... 4.85 parts by weight 4,4'-diazidostilbene-2,2'-disulfonic acid disodium salt ... 0.15 parts by weight Water: 95 parts by weight Surfactant (LT-221 manufactured by NOF Corporation): 0.2 parts by weight Silane coupling agent: KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd .: 0.25 parts by weight Black matrix obtained as described above For the plate (Sample 1-8, Comparative Samples 1 to 5), a black matrix of resolution (line and space), and the optical density O
D was measured. The measurement results are shown in Table 1 below together with the optimum exposure amount at the time of preparing each sample.

[0045]

[Table 1] As shown in Table 1, Samples 1 to 8 exhibited a high resolution of 10 μm or less and a high optical density of 3 or more, and had the characteristics required for the black matrix substrate. On the other hand, Comparative Samples 1 to 5 have a resolution exceeding 10 μm,
Further, the optical density OD was also less than 2, and it was not usable as a black matrix substrate.

Next, a colored layer, a protective layer and a transparent electrode were formed on each of the above black matrix substrates (Samples 1 to 8 and Comparative Samples 1 to 3) to prepare a color filter. Since black matrix substrates could not be obtained for Comparative Samples 4 to 5, the production of color filters was omitted.

The colored layer was formed with a plate depth of 6 μm and a width of 110 μm.
The following ink compositions S = 1, S-2, and S-3 are provided in this order between the black matrixes on the black matrix substrate by the intaglio offset printing method using a plate having m-shaped striped recesses and a silicone blanket. Printed and 110μ of blue, green and red respectively
An m-wide stripe pattern was formed by printing. Then, the above substrate was heated at 200 ° C. for 30 minutes to thermally cure the ink composition to obtain a colored layer having a thickness of 2 to 3 μm. (Composition of varnish) Polyester acrylate resin (Aronix M-7100 manufactured by Toagosei Kagaku Kogyo Co., Ltd.) 70 parts by weight Dialyl phthalate prepolymer 30 parts by weight (composition of ink composition (S-1)) Varnish … 100 parts by weight ・ Pigment (Rionol Blue ES) (Toyo Ink Mfg. Co., Ltd., CI Pigment Blue 15: 6)… 15.5 parts by weight ・ Pigment (Rionogen Violet RL) (Toyo Ink Mfg. Co., Ltd.) , CIPigment Violet 23) 4 parts by weight (composition of ink composition (S-2))-varnish 100 parts by weight-Pigment (Rionol Green 2YS) (CIPigment Green 36, manufactured by Toyo Ink Mfg. Co., Ltd.) 22 Parts by weight-Pigment (Seika Fast Yellow 2700) (CIPigment Yellow 83, manufactured by Dainichi Seika Kogyo Co., Ltd.) 7.5 parts by weight (composition of ink composition (S-3))-Varnish 100 parts by weight-Pigment (Chromophtal red A3B) (CIPigment Red 177, manufactured by Ciba Geigy) ... 32 parts by weight-Pigment (Seika Fast Yellow 2700) (CIPigment Yellow 83, manufactured by Dainichiseika Co., Ltd.) 8 parts by weight Next, in forming the protective layer, first, a coating solution having the composition shown below was applied onto the above colored layer by a spin coating method (rotation speed = 1500 rpm) (film thickness = 2. 0 μm). (Composition of coating liquid for forming protective layer) Photo-curable acrylate oligomer (o-cresol novolac epoxy acrylate (molecular weight 1500 to 2000) ... 35 parts by weight Cresol novolac type epoxy resin ... 15 parts by weight Polyfunctional polymerizable monomer (Dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) ... 50 parts by weight-Polymerization initiator (Irgacure manufactured by Ciba Geigy) ... 2 parts by weight-Epoxy curing agent (UVB1014 manufactured by General Electric Co.) ... 2 By weight: Ethyl cellosolve acetate: 200 parts by weight Then, the entire surface of the coating film was exposed at an exposure amount of 150 mJ / cm ² by using a proximity exposure apparatus, and then the substrate was cooled to 1,1,2 at room temperature. Immerse in 1,2-tetrachloroethane for 1 minute to remove only the uncured part of the coating film and protect layer Was formed.

Further, a 0.4 μm thick indium tin oxide (ITO) film was formed on the protective layer by a sputtering method.
A film was formed to form a transparent electrode, and a color filter was obtained.

Among the color filters thus manufactured, those manufactured by using the black matrix substrate (Samples 1 to 8) exhibited a high coloring effect and display contrast when used in a color liquid crystal display. However, those produced using the black matrix substrate (Comparative Samples 1 to 3) had insufficient coloring effect and display contrast when used in a color liquid crystal display.

[0050]

As described above in detail, according to the present invention, it is possible to obtain a black matrix substrate having a high resolution and a high optical density and a low reflectance and a good dimensional accuracy even when the proximity exposure is adopted. Further, since a vacuum process or the like is unnecessary, it is possible to reduce the manufacturing cost.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of an active matrix type liquid crystal display using a black matrix substrate manufactured according to the present invention.

FIG. 2 is a schematic sectional view of the liquid crystal display shown in FIG.

FIG. 3 is an enlarged partial sectional view of a color filter used in the liquid crystal display shown in FIG.

FIG. 4 is a process chart for explaining an example of a method of manufacturing a black matrix substrate according to the present invention.

FIG. 5 is a process drawing for explaining another example of the method for manufacturing a black matrix substrate according to the present invention.

[Explanation of symbols]

5, 8 ... Relief containing catalyst 9 ... Photomask for black matrix 10 ... Color filter 12 ... Black matrix substrate 13 ... Transparent substrate 14 ... Black matrix (light-shielding layer) 16 ... Colored layer 16R, 16G, 16B ... Coloring pattern

Continuation of front page (56) Reference JP-A-5-303090 (JP, A) JP-A-58-199342 (JP, A) JP-A-6-75110 (JP, A) JP-A-57-27258 (JP , A) JP-A-5-333551 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G02B 5/20 101

Claims (8)

(57) [Claims] 1. A photosensitive resin layer formed on a transparent substrate,
It is exposed and developed through a photomask having a black matrix pattern to form a relief on the transparent substrate, and the transparent substrate is brought into contact with an aqueous solution of a metal compound which serves as a catalyst for electroless plating to remove the metal compound from the relief. In the method for producing a black matrix substrate, the light-shielding layer having a pattern for black matrix is formed by contacting the catalyst-containing relief with an electroless plating solution. Are α-substituted acrylamides, N-monosubstituted acrylamides, N-substituted acrylamides,
Water-soluble resin having a polymer using at least one monomer selected from the group of acrylamide-based monomers consisting of N-di-substituted compounds and N-mono-substituted methacrylamides, and a cross-linking agent having a water-soluble azide compound A method for producing a black matrix substrate, which is formed by using a water-soluble photosensitive resin composition containing a. 2. The method for producing a black matrix substrate according to claim 1, wherein the polymer is a copolymer using two or more kinds of monomers. 3. The method for producing a black matrix substrate according to claim 2, wherein the copolymer is a copolymer using only the acrylamide-based monomer. 4. The method for producing a black matrix substrate according to claim 1, wherein the polymer is a homopolymer using one kind of monomer. 5. A photosensitive resin layer containing a metal compound serving as a catalyst for electroless plating formed on a transparent substrate is exposed and developed through a photomask having a pattern for a black matrix to form a transparent resin on the transparent substrate. In the method for producing a black matrix substrate, which comprises forming a catalyst-containing relief, and then forming a light-shielding layer having a pattern for black matrix by contacting the catalyst-containing relief with an electroless plating solution, the photosensitive resin layer is acrylamide. Α-substituted product of acrylamide, N-monosubstituted product of acrylamide, N of acrylamide,
Water-soluble resin having a polymer using at least one monomer selected from the group of acrylamide-based monomers consisting of N-di-substituted compounds and N-mono-substituted methacrylamides, and a cross-linking agent having a water-soluble azide compound A method for producing a black matrix substrate, which is formed by using a water-soluble photosensitive resin composition containing a. 6. The method for producing a black matrix substrate according to claim 5, wherein the polymer is a copolymer using two or more kinds of monomers. 7. The method for manufacturing a black matrix substrate according to claim 6, wherein the copolymer is a copolymer using only the acrylamide-based monomer. 8. The method for producing a black matrix substrate according to claim 5, wherein the polymer is a homopolymer using one kind of monomer.