JPH06258520A - Black matrix substrate - Google Patents

Abstract

PURPOSE:To provide a black matrix substrate having not only high dimensional accuracy but also high optical density and low reflectance which can be used for a flat display such as a liquid crystal display, an imager such as CCD, or a color filter such as a color sensor. CONSTITUTION:This black matrix substrate 12 consists of a substrate 13 and a black pattern 14 containing at least metal particles formed on the substrate 13. The metal particles have such a distribution of particle size that >=80% of the whole particles are in the range of 5-50nm particle size, and have >=60% projection area density in terms of 600Angstrom -thick particles and >=1.5 optical density.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black matrix substrate, and more particularly to 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. The liquid crystal display includes an active matrix system and a simple matrix system for controlling the three primary colors, and a color filter is used in each system. In the liquid crystal display, the constituent pixel portions have three primary colors (R, G, B), and the electrical switching of the liquid crystal controls the transmission of each light of the three primary colors to perform color display.

This color filter is formed by forming each colored layer, a protective layer and a transparent electrode layer on a transparent substrate. Then, in order to improve the coloring effect and the display contrast, a pattern (black matrix) having a light-shielding property is formed at the boundary portion of each pixel of R, G and B 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 a light leak current due to external light. Therefore, the black matrix is required to have a high light-shielding property.

Conventionally, as a black matrix, a chrome thin film formed by vapor deposition, sputtering or the like is photo-etched to form a relief, a hydrophilic resin relief is dyed, and a relief is formed using a photosensitive solution in which a black pigment is dispersed. There were those formed by electrodeposition of a black electrodeposition coating, those formed by printing, and the like.

[0005]

However, the chrome thin film formed by photo-etching to form a relief has a high dimensional accuracy because it uses a photo process, but a vacuum film forming process such as vapor deposition or sputtering is required. In addition, since the manufacturing process is complicated, the manufacturing cost is high, and it is necessary to suppress the reflectance on the observer side in order to increase the display contrast under strong external light, which further increases the manufacturing cost. It was necessary to sputter low-reflectance chromium. Further, the method of using the photosensitive resist in which the black dye or pigment is dispersed in advance described above, the manufacturing cost is low, but since the photoprocess is likely to be insufficient because the photosensitive resist is black, it is sufficient to attach importance to dimensional accuracy. There is a problem that it is difficult to obtain a high quality black matrix, for example, it is difficult to obtain a high light-shielding property. Further, in the black matrix formation by the above-mentioned printing method, although the manufacturing cost can be reduced, there is a problem when high dimensional accuracy is required.

The present invention has been made in view of the above circumstances, and has a high dimensional accuracy and can be used for a flat display such as a liquid crystal display, an imager such as a CCD, or a color filter such as a color sensor. An object of the present invention is to provide a black matrix substrate having excellent properties and low reflection.

[0007]

In order to achieve these objects, the present invention provides a substrate and a substrate formed on the substrate.
A black matrix substrate having at least a black pattern containing metal particles therein, wherein the metal particles have a particle size range of 5 to 50 nm in an amount of 80% of all particles.
It has a particle size distribution as described above, the projected area density of the particles in terms of 600Å thickness is 60% or more, and the optical density is 1.5 or more.

[0008]

The metal particles are deposited in a preformed resin pattern containing a catalyst component, and the metal particles have a particle size of 5
Since the particles in the range of ˜50 nm have a particle size distribution such that they are 80% or more of the total particles, the projected area density of the particles is 60% or more, and the optical density is 1.5 or more, it is possible to form a pattern. However, if a photosensitive resin or an electron beam resist is used, there is an advantage that the dimensional accuracy is high, and even a thin film has an excellent light-shielding property, and a black matrix substrate having low reflection from the observer side is formed.

[0009]

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 comprises a black relief (black matrix) 14 on a transparent substrate 13.
Forming a black matrix substrate 12 and a black matrix 14 of the black matrix substrate 12.
The colored layer 16 formed between them, and the protective layer 18 provided so as to cover the black matrix 14 and the colored layer 16.
And a transparent electrode 19. 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 the red pattern 16
It is composed of R, green pattern 16G, and 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 and 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 where the illumination light is irradiated from the polarizing plate 51 side. 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.

As shown in FIG. 5, the black matrix substrate 12 constituting such a color filter 10 has a substrate 13 and a black pattern 14 (formed on the substrate 13 and containing at least metal particles therein). Black relief or black matrix).

As the substrate 13, a transparent substrate or a substrate having a reflecting portion is used. As the transparent substrate, a rigid material such as quartz glass, borosilicate glass, soda lime glass or low expansion glass, or a flexible material such as a transparent resin film or an optical resin plate is used. be able to. 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. Matrix type L
Since it is used as a substrate for a CD, it is suitable for facing color filters. Further, for applications such as reflection projection type, a metal reflective film may be formed on one side of the transparent substrate, or a metal reflective film may be used for a display electrode of a thin film transistor or an active matrix on a silicone substrate. Is also good. When a substrate having a reflection portion is used, it becomes a black matrix substrate for a reflection type color filter, and is suitable for a reflection projection type, guest host or scattering type display mode.

The black pattern 14 has a resin (hereinafter, referred to as a resin pattern) formed in a predetermined pattern shape, and metal particles contained in the resin. Such a black pattern 14 is formed by depositing metal particles in a resin pattern containing a catalyst component by electroless plating using a reducing agent capable of reducing metal ions in an electroless plating solution. . As the resin used for the resin pattern, a resin that can be formed by a printing method or a photolithography method can be applied. As the resin used in the printing method, for example, in the case of intaglio offset printing, various known gravure inks can be used. In this case, the ink may contain a catalyst component described below in advance, or the catalyst component may be impregnated in an ionic state in a later step and then reduced to impart catalytic activity. The resin used in the photolithography method will be described in detail later along with the process.

The metal particles contained in the black pattern 14 have a particle size distribution such that the particles having a particle size in the range of 5 to 50 nm account for 80% or more of all particles, and more preferably have a particle size of 10 to 3.
Those having a particle size distribution such that the particles in the range of 0 nm are 80% by weight or more of the total particles, and more preferably the particles in the range of 10 to 20 nm are 80% or more of the total particles. However, it is particularly suitable for increasing the optical density while keeping the reflectance low. When the number of particles having a particle size distribution of more than 50 nm does not exist, the metal particles not only have reflectivity but also form a continuous film on the film surface, and the film surface is covered with the continuous film. The inconvenience of suppressing the reaction occurs. On the other hand, if such particles do not have such a particle size distribution and there are many particles of less than 5 nm, the optical density (1.5 or more) required for the black matrix cannot be obtained. The grain size referred to in the present invention is, for example, 100 from a TEM cross-sectional photograph of a black matrix section.
This is a value obtained by measuring the sample diameter of each piece and statistically processing.

Furthermore, the metal particles contained in the black pattern 14 have a projected area density of 60% in terms of 600Å thickness.
As described above, it is necessary that it is 80% or more, and the optical density is 1.5 or more. 600Å of particles
If the projected area density in terms of thickness is less than 60%, the required optical density cannot be obtained even if the particle diameter is within the above-specified range. The optical density further relates to the thickness of the film of the black pattern 14, and the thickness is set so that the optical density is 1.5 or more. When the optical density is less than 1.5, the black matrix has insufficient light-shielding properties. In addition,
As shown in FIG. 8, the projected area density of the particles in terms of 600 Å thickness is obtained by slicing the black pattern 14 with a width of 600 Å using an ultramicrotome in the thickness direction (FIG. 8 (a)). 14a is obtained by observing it with a transmission electron microscope from the slice plane direction (FIG. 8).
(B)). In addition, as an example of a specific measuring method, the thickness of the slice was measured by a multi-differential interference microscope or the like, and a thickness close to 600 Å was selected and used. Note that it is difficult to slice with a thickness of 600Å, and if the thickness sliced with a thickness close to that is taken as t (Å) and the measured value of the projection density d (%) is obtained at this time, 600Å The thickness is converted into the projected area density D (%) by the following formula.

[0018]

[Equation 1] The particle size of the metal particles is, for example, the plating bath temperature during the plating reaction in the method for producing the black matrix substrate or the pH of the plating solution, the concentration of the catalyst treatment solution when the stirring solution of the plating solution is stirred, and the treatment time. It can change depending on the factors. The reflectance of at least one of the reflectances of the black pattern 14 on the substrate side and the black pattern surface side is 30% or less, and more preferably 15% or less. When the reflectance exceeds 30%, the display contrast cannot be sufficiently obtained because the reflection by the external light hinders the visibility.

An example of the manufacture of such a black matrix substrate 12 of the present invention is shown in FIG. 4 and will be described below with reference to this drawing. The resin pattern is formed by the photolithography method. First, a photosensitive resist containing a hydrophilic resin is applied on the substrate 13 to form a photosensitive resist layer 3 having a thickness of about 0.1 to 5.0 μm (FIG. 4 (A)). Next, the photosensitive resist layer 3 is exposed through the photomask 9 for black matrix (FIG. 4 (B)). Then, the exposed photosensitive resist layer 3 is developed to form a relief 4 (resin pattern) having a pattern for a black matrix (FIG. 4C). Next, this transparent substrate 1
3 is subjected to heat treatment (90 to 130 ° C., about 5 to 60 minutes), the relief 4 is dipped in an aqueous solution of a metal compound as a catalyst component which serves as a catalyst for electroless plating, washed with water, and a relief containing catalyst 5 ( (Catalyst-containing resin pattern) (FIG. 4)
(D)). Then, the catalyst-containing relief 4 on the transparent substrate 13 is brought into contact with an electroless plating solution to form a black pattern (black relief) 14, and the black pattern is further subjected to a film hardening treatment by heating or applying a hardening agent to obtain a black pattern. The matrix substrate 12 is formed (FIG. 4).
(E)). The heat treatment may be performed after the catalyst-containing relief is formed.

In the example shown in FIG. 6, first, a photosensitive resist containing a hydrophilic resin and an aqueous solution of a metal compound serving as a catalyst for electroless plating is applied onto the substrate 13 to a thickness of 0.
A photosensitive resist layer 6 having a thickness of about 1 to 5.0 μm is formed (FIG. 6A). Next, the photosensitive resist layer 6 is exposed through the photomask 9 for black matrix (FIG. 6 (B)). Then, the exposed photosensitive resist layer 6 is developed and dried to form a relief image 7 (catalyst-containing resin pattern) of the present invention having a pattern for a black matrix (FIG. 6 (C)). Unlike the relief image 4 shown in FIG. 4, the relief image 7 in this case is a catalyst-containing relief (catalyst-containing resin pattern) containing a metal compound serving as a catalyst for electroless plating.

Relief image 7 created as described above
In order to form the black pattern (black matrix) 14 by using, the relief image 7 is first subjected to heat treatment (9
0 to 130 ° C. for 5 to 60 minutes), and then the substrate 13
By bringing the above relief image (catalyst-containing relief) 7 into contact with an electroless plating solution, metal particles are deposited in the relief to be blackened to form a black pattern (black matrix) 14 (FIG. 6 (D)). ). Also in this case,
It goes without saying that the black matrix may be subjected to a film hardening treatment by heating or applying a film hardening agent.

Further, in the example shown in FIG. 7, first, a photosensitive resist containing a hydrophilic resin, a compound having a diazo group or an azide group, and a metal compound serving as a catalyst for electroless plating is formed on the transparent substrate 13. Coating and drying to a thickness of 0.
A photosensitive resist layer 8 having a thickness of 1 to 5.0 μm, preferably 0.1 to 2.0 μm is formed (FIG. 7A). Here, a compound having a diazo group or an azido group has an effect of suppressing plating during electroless plating. Using a resist containing these, a hydrophilic resin, and a compound that serves as a catalyst for electroless plating, pattern exposure and electroless plating are performed. It is known that electroless plating metal particles are formed in the resist layer to form a light-shielding layer by contact with a liquid (JP-A-57-1049).
28, 57-104929). Then, the photosensitive resist layer 8 is exposed through a photomask 9 for a black matrix to form a relief image 8'of the present invention (FIG. 7 (B)). That is, this relief image 8 '
Is a catalyst-containing relief containing a metal compound serving as a catalyst for electroless plating, and the plating suppressing effect by the compound having a diazo group or an azide group is released to the pattern shape of the black matrix by the above exposure. ing.

To form the black matrix 14 using the relief image 8'created as described above, the substrate 13 is brought into contact with an electroless plating solution to deposit metal particles for electroless plating on the exposed portion. Then, it is blackened to form a black matrix 14 (FIG. 7).
(C)).

Incidentally, as shown in FIG. 7D, the unexposed portion may be developed and removed. In the manufacturing examples of the black matrix substrate described above, the common characteristic is that the reaction does not occur at a bath temperature of about 20 ° C. to 40 ° C. instead of the reaction at a bath temperature of about 70 ° C. to 90 ° C. as in conventional electroless plating. In the presence of a metal compound serving as a catalyst for electrolytic plating, the reducing agent capable of reducing the metal compound and the reducible metal salt contained in the electroless plating solution reduces the reduction of the reducible metal salt by a conventional method. Compared with electrolytic plating, the metal particles are deposited and grown slowly in the resist (resin) by being performed at an extremely low speed, and the metal particles are uniformly deposited in the black pattern (light-shielding layer).

Therefore, the black pattern includes metal particles and a metal salt to be reduced in some cases, a metal compound to be electroless plated and, in some cases, a metal produced by reducing the metal compound, and a reducing agent. Contains.

Examples of the photosensitive resist used in the present invention include natural proteins such as gelatin, casein, glue and egg albumin, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide and maleic anhydride. For the copolymer and a mixture of one or more hydrophilic resins such as carboxylic acid modified products or sulfonic acid modified products of the above resins, for example, a diazonium compound having a diazo group and paraformaldehyde Reaction product diazo resin, azide compound having azido group, cinnamic acid condensation resin obtained by condensing cinnamic acid with polyvinyl alcohol, resin using stilbazolium salt, photocurable photosensitive group such as ammonium dichromate Have It may be mentioned those obtained by imparting photosensitivity by adding one. Needless to say, the photosensitive group is not limited to the above photocurable photosensitive group. As described above, since the photosensitive resin contains the hydrophilic resin, the electroless plating solution penetrates into the catalyst-containing relief 5 when the catalyst-containing relief 5 comes into contact with the electroless plating solution as described above. The metal particles can be uniformly deposited and grown in the catalyst-containing relief 5.

The metal compound used as a catalyst for electroless plating used in the present invention includes chlorides such as palladium, gold, silver, tin, zinc, platinum and copper, water-soluble salts such as sulfates and nitrates, and complex compounds. Is used. In particular, in the present invention, an activator solution for electroless plating, which is commercially available as an aqueous solution, can be used as it is or after being diluted. When such a metal compound is contained in the photosensitive resist as described above, it is 0.0 in terms of metal ion.
It is preferable that the content is about 1 to 5% 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,
Water-soluble reducible heavy metal salts such as iron, copper, chromium, palladium, gold, platinum, tin, and zinc (which form metal ions in the plating solution), and water that improves the plating rate, reduction efficiency, etc. Basic compounds such as sodium oxide, potassium hydroxide and ammonium hydroxide, pH adjusting agents such as inorganic acids and organic acids, oxycarboxylic acids such as sodium citrate and sodium acetate, boric acid, carbonic acid, organic acids and inorganic acids An electroless plating solution having a buffering agent typified by the alkali salt and a complexing agent for the purpose of stabilizing heavy metal ions, a reaction accelerator, a stabilizer, a surfactant and the like is used. The electroless plating solution as described above preferably has a pH value of 6 to 9 and a plating solution temperature of 20 to 40 [deg.] C. in order to control the reaction rate.

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

Among the various reducing agents mentioned above, a boron-based reducing agent, in particular, is a metal compound which serves as a catalyst for electroless plating,
It has an excellent ability to simultaneously reduce reducible metal salts,
It can be preferably used.

Black matrix substrate 1 as described above
The colored layer 16 formed of the red pattern 16R, the green pattern 16G, and the blue pattern 16B between the two black matrices 14 is formed by a photoresist dyeing method or a photolithographic method after applying a photosensitive resin in which a pigment is dispersed in advance. It can be carried out according to various known methods such as a dispersion method, a printing method such as offset, and an electrodeposition method.

A protective layer 18 may be provided so as to cover the black matrix 14 and the colored layer 16 of the color filter 10 to smooth the surface of the color filter 10, improve reliability and prevent contamination of the liquid crystal layer 40. It is intended, and a transparent resin such as an acrylic resin, a urethane resin, a polyester resin, an epoxy resin, a polyimide resin, or the like, and particularly a heat or light curable transparent resin is preferably used. Alternatively, it can be formed using a transparent inorganic compound such as silicon dioxide. The thickness of the protective layer is 0.
It is preferably about 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 or a sputtering method, and the thickness thereof is preferably about 200 to 2000 angstrom.

Next, the present invention will be described in more detail with reference to experimental examples. (Preparation of Inventive Sample 1) As a transparent substrate, a 100 μm-thick polyester film (Lumirror T / 100 manufactured by Toray) that had been plasma-treated in advance was adhered to glass. On the polyester film of this substrate, spin coat method (1500 r.
pm) to a thickness of 0.6 μm. Then, it dried at 70 degreeC for 10 minute (s), and formed the photosensitive resist layer.

Photosensitive resist composition Polyvinyl alcohol (Nippon Gosei Kagaku: Gohsenal T-330) 4.47% aqueous solution ... 100 parts by weight Diazo resin (Shinko Giken D-011) 4.47% aqueous solution ... 5.71 Parts by weight Next, the transparent film having the photosensitive resist layer is removed from the glass and a photomask for forming a black matrix is formed on the photosensitive resist layer (negative, line width = 20 μm).
Exposure was carried out through. An ultra-high pressure mercury lamp 2 Kw was used as a light source, and irradiation was performed for 2 seconds. Then, spray development was performed using water at room temperature and air drying was performed. Then, this transparent film was subjected to heat treatment at 100 ° C. for 30 minutes to form a relief for a black matrix having a line width of 20 μm.

Next, this transparent film was treated with an aqueous solution of palladium chloride (5-fold diluted Red Schumer manufactured by Nippon Kanigen).
After immersing in water for 2 minutes, rinsing with water and draining, immersing in a nickel plating solution containing a boron-based reducing agent at 30 ° C. (Nickel plating solution Top Chemialoy B-1 manufactured by Okuno Seiyaku Co., Ltd.) for 4 minutes, rinsing and drying, and a light-shielding layer ( Black matrix) was formed to obtain a black matrix substrate. (Production of Inventive Sample 2) Inventive Sample 2 was produced in the same manner as Inventive Sample 1 except that the plating time of Inventive Sample 1 was changed from 4 minutes to 10 minutes. (Production of Inventive Sample 3) Inventive Sample 3 was produced in the same manner as Inventive Sample 1 except that the plating time of Inventive Sample 1 was changed from 4 minutes to 15 minutes. (Preparation of Inventive Sample 4) The steps up to the relief forming step are performed in the same manner as in Inventive Sample 1 described above, and then a catalytically active liquid is added to an aqueous palladium chloride solution (a 50-fold dilution solution of Red Schumer manufactured by Nippon Kanigen) for about 2 minutes. After dipping, washing with water and draining, dipping in a room temperature nickel plating solution (nickel plating solution Top Chemialoy B-1 manufactured by Okuno Seiyaku) containing a boron-based reducing agent for 9 minutes, washing with water and drying to form a black pattern (black matrix). Then, a black matrix substrate was obtained. (Production of Inventive Sample 5) Inventive Sample 5 was produced in the same manner as Inventive Sample 4 except that the plating time of Inventive Sample 4 was changed from 9 minutes to 35 minutes. (Preparation of Comparative Sample 1) Comparative Sample 1 was prepared in the same manner as Sample 1 of the present invention except that the plating time of Sample 1 of the present invention was changed from 4 minutes to 1 minute. (Preparation of Comparative Sample 2) Comparative Sample 2 was prepared in the same manner as Sample 1 of the present invention except that the plating time of Sample 1 of the present invention was changed from 4 minutes to 2 minutes. (Preparation of Comparative Sample 3) Comparative Sample 3 was prepared in the same manner as Sample 4 of the present invention except that the plating time of Sample 4 of the present invention was changed from 9 minutes to 3 minutes. (Preparation of Comparative Sample 4) Comparative Sample 4 was prepared in the same manner as Sample 4 of the present invention except that the plating time of Sample 4 of the present invention was changed from 9 minutes to 6 minutes.

These nine samples (invention sample 1)
.About.5, Comparative Samples 1 to 4), the particle size and projected area density of the nickel fine particles deposited in the black pattern (light-shielding layer) were measured by a transmission electron microscope (Hitachi Ltd.,
H-8100).

Furthermore, the optical density (OD) of the black matrix and the reflectance (R) at a wavelength of 555 nm were measured by a microspectroscope (Olympus Optical Co., AH2-SRK / ST).
According to (K), the specular reflection light was measured for the light which is incident almost perpendicularly to the substrate. In addition, the optical density of the black matrix is as follows, when the transparent substrate is used as a reference (100% transmittance) and the light is completely blocked by the above-mentioned device.
Lowest transmittance T in the visible region of 400 to 700 nm measured with the background (0% transmittance) as a reference value
(%) Was calculated by the calculation of OD = −log (T / 100). In addition, the reflectance was measured with the aluminum vapor deposition plate as a background serving as a reference and the case where no reflecting object was present as a reference value. Further, as the reflectance, a value when light was irradiated from the substrate side of the black pattern 14 (observer side), a value when light was irradiated from the surface (film surface) side of the black pattern, and two types of reflectance were measured. .

The measurement results are shown in Table 1 below. The optical density of 3 or more has a transmittance of 0.1% or less, and there is no significant difference in the value of 0.1% or less, so that it is described as OD ≧ 3.

[0040]

[Table 1] As can be seen from the results of Table 1, Samples 1 to 5 of the present invention
Is 80% or more of all particles having a particle diameter of 5 to 50 nm, and the projected area density of particles is 6
Since it is 0% or more, the reflectance on the observer side (the side opposite to the film surface) is significantly lower than that of conventional metal chrome (reflectance of 60% or more), and the optics necessary as a black pattern light-shielding layer. The density (1.5 or more) was sufficiently obtained, which was an extremely excellent black matrix substrate. In particular, the sample 1 of the present invention had a good reflectance from the film surface side. In contrast, comparative samples 1 and 3
The nickel particles have an average particle size of more than 5 nm, but 20% or more of all the particles are less than 5 nm and the projected area density of the particles is 20% or less. Although the reflectance is low, the black pattern (black matrix The optical density required to obtain the original function of the light-shielding layer in 1) was not sufficiently obtained, and it was insufficient as a black matrix substrate (this can be sufficiently confirmed by visual observation). In Comparative Samples 2 and 4, the average particle diameter of nickel particles was 9.3 nm and 14.1 n, respectively.
m, and the number of particles having a particle size in the range of 5 to 50 nm is 80% or more of all the particles. Although these are within the definition of the present invention, the projected area density of the particles is less than 60% (5
7.3% and 54.0%), so that a sufficient optical density was not obtained, and like the comparative samples 1 and 3, this was also insufficient as a black matrix substrate. .

Next, a black pattern was formed on the glass substrate under the same conditions as those of Sample 1 of the present invention. Using this black matrix substrate, a color filter was produced in the following manner.

That is, the following ink composition S-1 was used between the black matrix on the black matrix substrate by the intaglio offset printing method using a plate having a stripe-shaped recess having a plate depth of 6 μm and a width of 110 μm and a silicone blanket. S-2 and S-3 were printed in this order to form blue, green and red stripe patterns having a width of 110 μm, respectively. Then, the ink composition was thermally cured by heating the substrate at 200 ° C. for 30 minutes to obtain a colored layer having a thickness of 2 to 3 μm.

Composition of varnish Polyester acrylate resin (Aronix M-7100, Toagosei Kagaku Kogyo KK) 70 parts by weight Diallyl 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., CI Pigment) Vioet 23) 4 parts by weight Composition of ink composition (S-2) Varnish 100 parts by weight Pigment (Rionol Green 2YS) (CIPigmentGreen 36 manufactured by Toyo Ink Mfg. Co., Ltd.) 22 parts by weight Pigment ( Seika Fast Yellow 2700) (Dainichiseika Color & Chemicals Mfg. Co., Ltd., CI Pigment Yellow 83) ... composition varnish ... 100 weight 7.5 parts by weight ink composition (S-3)・ Pigment (Chromophtal red A3B) (Ciba Geigy Co., CIPigment Red 177) 32 parts by weight ・ Pigment (Seikafe Stello 2700) (Dainichi Seika Chemicals Co., Ltd., C..Pigment Yellow 83) ... 8 parts by weight Next, a protective layer and a transparent electrode were formed as described above to obtain a color filter.

That is, the formation of the protective layer was carried out by spin coating a coating solution having the composition shown below (rotation speed = 1500 r.m.).
pm) was applied on the above colored layer (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 Functionally polymerizable monomer (dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku)) 50 parts by weight Polymerization initiator (Irgacure manufactured by Ciba Geigy) 2 parts by weight Epoxy curing agent (UVE1014 manufactured by General Electric) 2 By weight: Ethyl cellosolve acetate: 200 parts by weight And, for this coating film, an exposure amount of 150 mJ was used by using a proximity exposure device manufactured by Dainippon Screen Co., Ltd.
The whole surface was exposed at / cm ² . After that, the substrate is
It was immersed in 1,2,2-tetrachloroethane for 1 minute to remove only the uncured portion of the coating film to form a protective film.

Further, a 0.4 μm thick indium tin oxide (ITO) film is formed on the protective film by a sputtering method.
A film was formed to form a transparent electrode, and a color filter was obtained. An LCD panel was produced using the color filter thus produced and a TFT substrate formed by a known method.

Amorphous silicon was used for the semiconductor layer of the TFT substrate, and the polarizing plate of the LCD was attached so as to be normally white. In order to evaluate the characteristics of this LCD, the relationship between the gate voltage and the transmittance of the LCD was measured.

As a result, in the LCD using the color filter according to the present invention, the LC using the conventional color filter using Cr as the black matrix layer is used.
It was found that the gate-off voltage can be reduced by 2 V as compared with D.

This is because when the conventional color filter is used, the reflectance of the black matrix layer of the color filter is high, so that part of the light of the backlight of the LCD is reflected on the surface of the black matrix layer. , TFT
The incident light is incident on the TFT and causes the generation of photocurrent in the TFT. On the other hand, in the color filter using the black matrix substrate of the present invention, the reflectance to the surface of the black matrix layer is low, and It is presumed that the irradiation dose is reduced, and as a result, the photocurrent of the TFT is reduced and the gate-off voltage is improved.

From these results, LC using a color filter using the black matrix substrate according to the present invention
In D, the drive voltage of the LCD can be reduced, and an effect was recognized in reducing power consumption. This has a great effect on extending the continuous use time when the dry battery is driven.

Further, in order to evaluate another effect of the color filter according to the present invention, the contrast ratio of the LCD was measured. In contrast ratio measurement in a bright place, it was possible to obtain a contrast ratio 2.4 times that of the conventional color filter.

It is presumed that this is because the black matrix layer of the color filter has a low reflectance and the influence of external light is reduced. Further, even when the contrast ratio was measured in a dark place, when the color filter according to the present invention was used, a contrast ratio 1.6 times that of the conventional method could be obtained.

This is because when the color filter using the black matrix substrate of the present invention is used, the photocurrent of the TFT is reduced as described above, and as a result, the leakage light during black display is improved. It is estimated that this was done.

As described above, it was found that the color filter according to the present invention is effective in reducing the power consumption of the LCD and improving the contrast ratio.

[0055]

As described in detail above, according to the present invention, the metal particles contained in the black pattern have a particle size of 5 to 50 n.
The particle size distribution is such that the particles in the range of m are 80% or more of all particles, and the projected area density of the particles in terms of 600Å thickness is 6
Since it is 0% or more and the optical density is 1.5 or more, a black pattern (black matrix) having an optical density of 1.5 or more and a low reflectance can be obtained. When this is used for a liquid crystal display vise, the reflectance of the black matrix against the external light is suppressed to a low level, so that the visibility can be improved.
Furthermore, in the active matrix, by reducing the reflectance on the TFT substrate side, stray light in the liquid crystal can be reduced,
Leakage due to the light from the TFT can be reduced, and the power consumption of the LCD can be reduced and the contrast ratio can be improved.

[Brief description of drawings]

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

FIG. 5 is a schematic sectional view of a black matrix substrate of the present invention.

FIG. 6 is a process chart for explaining another method for manufacturing a black matrix substrate according to the present invention.

FIG. 7 is a process drawing for explaining another method for manufacturing a black matrix substrate according to the present invention.

FIG. 8 is a diagram schematically showing a method for measuring a projected areal density of particles. FIG. 8A is a view in which the peeled black pattern 14 is sliced in the thickness direction with a width of 600 angstroms, and FIG. 8B is a slice piece 14a.
FIG. 3 is a view of observing the sample with a transmission electron microscope from the slice plane direction.

FIG. 9: A black pattern produced as a sample 1 of the present invention was sliced in a thickness direction with a width of 600 Å,
It is a drawing substitute photograph which observed the slice piece from the slice surface direction with the transmission electron microscope. Shooting conditions Acceleration voltage: 200 KV Beam current: 10 μA Convergence movable diaphragm: 80 μm Objective movable diaphragm: 40 μm Direct magnification (shooting magnification): 20 K times Enlargement magnification (final magnification): 100 K times

FIG. 10 is a drawing-substitute photograph obtained by further magnifying the photograph of FIG. 9 by 5 times. Shooting conditions Acceleration voltage: 200 KV Beam current: 10 μA Convergent movable diaphragm: 80 μm Objective movable diaphragm: 40 μm Direct magnification (shooting magnification): 100 K times Enlargement magnification (final magnification): 500 K times

FIG. 11 is a drawing-substituting photograph obtained by slicing a black pattern produced as Sample 3 of the present invention in the thickness direction with a width of 600 Å, and observing the slice pieces with a transmission electron microscope from the slice plane direction. The shooting conditions are shown in Figure 9.
According to that.

12 is a drawing-substitute photograph obtained by further magnifying the photograph of FIG. 11 by a factor of 5. FIG. The shooting conditions were in accordance with those shown in FIG.

FIG. 13: A black pattern produced as a comparative sample 1 is sliced in a thickness direction with a width of 600 Å,
It is a drawing substitute photograph which observed the slice piece from the slice surface direction with the transmission electron microscope. The shooting conditions were the same as those shown in FIG.

FIG. 14 is a drawing-substitute photograph in which the photograph in FIG. 13 is further magnified five times. The shooting conditions were in accordance with those shown in FIG.

[Explanation of symbols]

3 ... Photosensitive resist layer 4 ... Relief (resin pattern) 5 ... Catalyst containing relief (catalyst containing resin pattern) 9 ... Photomask for black matrix 10 ... Color filter 12 ... Black matrix substrate 13 ... Substrate 14 ... Black pattern (black) Matrix, black relief or light-shielding layer) 16 ... Coloring layer 16R, 16G, 16B ... Coloring pattern

Claims (4)

[Claims] 1. A black matrix substrate comprising a substrate and a black pattern formed on the substrate and containing at least metal particles therein, wherein the metal particles have a particle size in the range of 5 to 50 nm. It has a particle size distribution that is more than 80% of all particles,
A black matrix substrate having a projected area density of 60% or more in terms of a thickness of 00Å and an optical density of 1.5 or more. 2. The metal particles are nickel, cobalt,
The black matrix substrate according to claim 1, which is at least one selected from the group consisting of iron, chromium, copper, palladium, gold, platinum, tin, and zinc. 3. The metal particles are electroless plated using a reducing agent capable of reducing the catalyst component contained in the resin pattern before black pattern formation and the metal ions in the electroless solution, The black matrix substrate according to claim 1 or 2, wherein the black matrix substrate is deposited in a resin pattern containing a catalyst component. 4. The black matrix substrate according to claim 1, wherein the reducing agent is a boron-based or phosphoric acid-based reducing agent.