KR102112520B1 - Black matrix substrate - Google Patents

Abstract

An object of the present invention is to provide a resin black matrix substrate on which a resin black matrix having a low optical reflectance and sufficient optical density is formed.
The present invention, in order, has a transparent substrate, a light-blocking layer (A) and a light-blocking layer (B), the optical density per thickness of the light-shielding layer (A) is lower than the optical concentration per thickness of the light-shielding layer (B), and the light-shielding layer ( A) is a black matrix substrate containing a light-shielding material and fine particles having a refractive index of 1.4 to 1.8.
The black matrix substrate of the present invention is useful for color filters and liquid crystal displays from its characteristics.

Description

Black Matrix Substrate {BLACK MATRIX SUBSTRATE}

The present invention relates to a black matrix substrate that can be used for color filters used in liquid crystal displays and light emitting devices.

The liquid crystal display device employs a structure in which a liquid crystal layer is sandwiched between two substrates, and expresses contrast using the electro-optical response of the liquid crystal layer, but color display is also possible by using a color filter substrate.

Conventionally, a black thin film formed on a color filter substrate and used as a light-shielding layer is mainly a metal thin film made of a chromium-based material, but a resin black matrix containing a resin and a light-shielding material has been developed to reduce cost and environmental pollution. A liquid crystal display device having a color filter substrate having a resin black matrix containing a light-shielding material such as carbon black has good visibility indoors, but when used outdoors, visibility due to reflection of external light originating from the black matrix Deterioration is a problem.

From these backgrounds, various studies have been conducted to realize a resin black matrix having a high optical density (hereinafter sometimes referred to as "OD value") and a low reflectance when viewed from the transparent substrate side. For example, a method of using black color fine particles whose surface is covered with an insulating material (Patent Document 1), a method of adding carbon black to titanium oxynitride (Patent Document 2), and a mixture of titanium nitride and titanium carbide are used. Method (Patent Document 3), a method comprising a two-layer structure of a colored relief layer and a black relief layer (Patent Document 4), and a method of forming a two-layer structure of a light absorbing layer and a reflective light absorbing layer containing fine anisotropic metal particles (Patent Document) 5) is being proposed.

Japanese Patent Publication 2001-183511 Japanese Patent Publication 2006-209102 Japanese Patent Publication 2010-95716 Japanese Patent Publication No. Hei 8-146410 Japanese Patent Publication 2006-251237

However, since the high light-shielding material has a high reflectance in principle, it has been very difficult to achieve both sufficient optical density and low reflectivity in the resin black matrix. In addition, there is also a problem that it is difficult to realize a low reflectance over the entire visible light region for the method of making the resin black matrix in a two-layer configuration, furthermore, it becomes highly conductive by using metal fine particles, and display failure due to electric field abnormality There is something that generates.

Accordingly, an object of the present invention is to provide a black matrix substrate having a resin black matrix having high optical density, low reflectivity and high resistance, while having high optical density.

The present invention provides the following black matrix substrate and the like.

(1) In order, it has a transparent substrate, a light-blocking layer (A) and a light-blocking layer (B),

The optical density per thickness of the light-shielding layer (A) is lower than the optical concentration per thickness of the light-shielding layer (B), and the light-shielding layer (A) contains a light-shielding material and fine particles having a refractive index of 1.4 to 1.8.

The present invention provides the following black matrix substrate as a preferred form of the invention.

(2) The fine particles having a refractive index of 1.4 to 1.8 are the above-mentioned black particles, which are one or more fine particles selected from the group consisting of aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, and sodium metasilicate. Matrix substrate.

(3) The black matrix substrate according to any one of the above, wherein the fine particles having a refractive index of 1.4 to 1.8 have a whiteness of 30% or more measured by a method in accordance with JIS P8148 (2001).

(4) The transparent substrate is any one of the black matrix substrates made of polyimide resin.

In addition, the present invention provides the following objects using the black matrix substrate.

(5) The color filter substrate in which the light-shielding layer (A) and the light-shielding layer (B) of any one of the black matrix substrates have a pattern shape, and there are pixels colored in portions where no pattern is present.

(6) A light emitting device having the color filter substrate and a light emitting element.

(7) The light-emitting device wherein the light-emitting element is an organic EL element.

(8) A liquid crystal display device having the color filter substrate, a liquid crystal compound and a counter substrate.

In addition, the present invention provides a preferred method for manufacturing the black matrix substrate and color filter as follows.

(9) Above the transparent substrate

A step of forming a layer of a composition containing a light-shielding material and a resin,

A step of forming a layer of a photosensitive resin composition containing a light-shielding material thereon,

A method for producing a black matrix substrate having a step of pattern-exposing the patterned layer of the two types with a developer or a solvent.

(10) A method of manufacturing a color filter having a process of forming a pixel where a pattern does not exist after manufacturing a black matrix substrate by the above method.

(Effects of the Invention)

According to the black matrix substrate of the present invention, since the light-shielding layer does not pass the light of the backlight, sufficient light-shielding property can be realized, and a clear image can be obtained with high contrast, and since the reflectance is low, visibility is also possible under external light. It becomes possible to obtain a liquid crystal display device which is very excellent and has high electrical reliability.

1 is a schematic cross-sectional view showing some embodiments of a black matrix substrate of the present invention.
2 is a schematic cross-sectional view showing an embodiment of the black matrix substrate of the present invention.
3 is a schematic cross-sectional view showing an embodiment of the light emitting device of the present invention.

The black matrix substrate of the present invention, in order, has a light-blocking layer (A) and a light-blocking layer (B) formed on a transparent substrate, and the optical density per thickness of the light-shielding layer (A) is the optical density per thickness of the light-shielding layer (B) It is characterized in that it is lower and the light-shielding layer (A) contains light-shielding material and fine particles having a refractive index of 1.4 to 1.8.

In general, it is known that the resin black matrix (hereinafter referred to as "resin BM") increases in reflectance as the optical density per thickness (optical density divided by thickness. Hereinafter referred to as "OD / T") increases. This is for the following reason.

In general, when two kinds of colorless transparent materials that face each other are in contact, the reflectance (R) of light incident on the interface can be represented by a difference in refractive index as shown in the following equation (1).

Reflectance (R) = (n ₁ -n ₂ ) ² / (n ₁ + n ₂ ) ² (1)

[Where n ₁ and n ₂ each represent the refractive index of any colorless transparent material (n ₁ , n ₂ )]

On the other hand, in the case of a colorless non-transparent material such as metal, the refractive index needs to be expressed as a complex refractive index,

The complex refractive index (N) = n-iκ (n represents the real part of the refractive index of the substance (n), κ represents the extinction coefficient) is used. When the colorless transparent material (m) and the colorless non-transparent material (n) are in contact, the reflectance (R) of light perpendicular to the interface from the material (m) side can be expressed as in Equation (2) below.

Reflectance (R) = {(mn) ² + κ ² } / {(m + n) ² + κ ² } (2)

[Where m represents the refractive index of the colorless transparent material (m), n represents the real part of the refractive index of the material (n), and κ represents the extinction coefficient of the material (n)]

According to this formula (2), it was found that the reflectance increases as the extinction coefficient (κ) increases. In addition, if the extinction coefficient (κ) is 0, that is, the substance (n) is colorless and transparent, the result is as in Equation (1).

By the way, the extinction coefficient is proportional to the extinction coefficient α at a certain wavelength. In addition, the absorption coefficient (α) can be approximated by multiplying OD / T by an integer. That is, since the extinction coefficient (κ) is proportional to the value of OD / T, when Equation (2) is used, as the OD / T increases, the reflectance (R) at the interface between the material (m) and the material (n) in principle increases. I knew it was getting higher.

The present inventors apply the material (m) of the formula (2) to the transparent substrate and the material (n) to the resin BM, so that the low reflectance and high light-shielding properties required as the properties of the resin BM are trade-offs under constant film thickness conditions. Estimated to be. It is effective to reduce the OD / T for low reflection, but in this case, it is necessary to increase the film thickness of the black matrix to ensure sufficient light shielding properties. The black matrix having a large film thickness causes alignment disorder of the liquid crystal and decreases contrast. Therefore, as a result of careful examination to solve this trade-off, a layer having a small OD / T above the transparent substrate, that is, a light-shielding layer (A), which can be referred to as a low-optical density layer, and a light-shielding layer (A) having OD / T ), A black matrix substrate having a light-blocking layer (B), which can be referred to as a layer having a larger optical density, that is, a high optical density layer, in this order has come to be considered suitable for solving the problem. In addition, the "light-shielding layer" referred to herein is not limited to blocking light 100%. According to the structure of this black matrix substrate, since the light-shielding layer A has a relatively low OD / T, reflection from the interface of the light-shielding layer A on the transparent substrate side is reduced for light coming from the transparent substrate side. Since the light is attenuated among the light-blocking layer A, the amount of reflection of light at the interface of the light-blocking layer A side of the light-blocking layer B is also reduced. As a result, the black matrix substrate of the present invention has a low reflectance. Moreover, since it has a light-shielding layer (B), it becomes possible to have sufficient light-shielding property with respect to the light transmitted through the light-shielding layer (B). That is, it is estimated that, by the configuration of such a black matrix substrate, it is possible to achieve both low reflection and sufficient light shielding properties for light from the transparent substrate side.

However, according to the examination of the present inventors, the interface of the layer having a large OD / T and the layer having a small OD / T by passing through the layer having a small OD / T through the light having entered the transparent substrate side only by setting it as described above. It has been found that reflections from and exist, and that it is not simple to realize the desired anti-reflection of the resin BM. Thus, the present inventors have found that in a black matrix substrate having such a configuration, the layer having a small OD / T contains both a light-shielding material and fine particles having a refractive index of 1.4 to 1.8, thereby achieving both sufficient light-shielding properties and low reflection. The invention has been completed.

The light-shielding layer (A) of the present invention has a layer configuration in which the optical density is not zero but is not substantially transparent, and its OD / T is smaller than the OD / T of the light-shielding layer (B). In addition, the light-blocking layer (B) of the present invention has a layer configuration in which the optical density is not zero but is not substantially transparent. In addition, the OD value referred to in the present invention is in the region of wavelength 380 to 700 nm.

OD value = log ₁₀ (I _O / I)

I ₀ : incident light intensity

I: transmitted light intensity

The average value of the values obtained in 5 nm units is used.

<< Light-shielding layer (A) >>

<Optical concentration>

The OD / T of the light-shielding layer (A) is preferably 0.5 µm ^-1 or more, and 1 µm ^-1 or more. In addition, this value is preferably 3㎛ ^-1 or less, and 2.5㎛ ^-1 or less. If this value is too small, the film thickness must be increased in order for the resin BM to be laminated to obtain a desired OD value. If this value is too large, the reflectance tends to be high. OD / T of the light-shielding layer (B) is preferably 3㎛ ^-1 or more, and 3.5㎛ ^-1 or more. Also, 8㎛ ^-1 or less, it is also preferred to 6㎛ ^-1 or less. If this value is too small, the film thickness becomes thick in order for the resin BM to obtain a desired OD value, and if it is large, a large amount of the light blocking material must be added, and pattern processing may be difficult.

The OD value of the entire light-blocking layer present on the black matrix substrate of the present invention is preferably 3 or more, and more preferably 4 or more. Moreover, 6 or less and 5 or less are more preferable. If the OD value of the whole is too low, the light of the backlight may partially pass and the contrast may decrease. On the other hand, if it is too high, the addition amount of the light-shielding material of the light-shielding layer (A) as well as the light-shielding layer (B) should be increased, and the reflectance tends to be higher when the desired film thickness is used.

The OD value of the light-shielding layer (A) is preferably 0.5 or more, and 0.8 or more, and more preferably 2.0 or less and 1.5 or less. The OD value of the light-shielding layer (B) is 1.5 or more, more preferably 2.0 or more, while 5.0 or less and more preferably 3.5 or less.

<Particulate>

It is preferable that the fine particles referred to in the present invention are not substantially colored and are pale, transparent or white. Pigments such as black pigments, red, blue, green, purple, yellow, magenta, or cyan are classified as light-shielding materials.

As a component of the fine particles, various ceramics, various resins, etc. may be mentioned in addition to those of white fine particles such as extender pigments or white pigments. However, it is necessary that the refractive index is 1.4 to 1.8 as described above.

The refractive index of the fine particles referred to herein is a refractive index in visible light, and as a representative value, a value of the refractive index at a wavelength of 589 nm corresponding to sodium D-ray can be adopted. As a method of measuring the refractive index, the fine particles themselves or a substance having the same composition as the fine particles can be measured as a sample using a liquid immersion method, that is, a Beckett method. As a method of obtaining the refractive index by the Beckett method, 30 samples of the same substance of the target fine particles are prepared, the refractive indexes are measured one by one, and the refractive index can be calculated by their average value.

It is necessary that the fine particles used in the present invention have a refractive index of 1.4 to 1.8, but preferably 1.5 to 1.7. The low refractive index means that, in principle, the density of the substances constituting the fine particles decreases. Therefore, such a low-density particle has a problem that it is easy to invade the organic solvent used as a dispersion medium when forming the light-shielding layer. In addition, the solvent resistance of the finished black matrix substrate is insufficient. On the other hand, if the refractive index is too high, since the refractive index of the light-shielding layer (A) is too large compared to the transparent substrate, reflection on the surface of the light-shielding layer (A) on the transparent substrate side becomes large, and consequently, the reflection of the black matrix substrate tends to be high. . According to the configuration of the present invention, since the fine particles having a refractive index in the above range are dispersed in a layer having a small OD / T, the effect of the incident light being scattered by the fine particles is minimized while reducing the refractive index of the layer having a small OD / T with a transparent substrate. It can be set to a close value, and it is presumed that the reflected light is attenuated together with the light blocking effect by the light blocking material.

Specific examples of the fine particles having a refractive index of 1.4 to 1.8 include resin fine particles such as acrylic resin, polyethylene resin, silicone fine particles, and fluorine resin. As a commercial item, as acrylic resin fine particles, Nippon Paint Co., Ltd. Production FS-101, FS102, FS106, FS-107, FS-201, FS-301, FS-501, FS-701, MG-155E, MG-451, MG-351, Toyobo Co., Ltd. Production "TAFTIC" (registered trademark) F-120, F-167 and the like.

As described above, the fine particles that can be used in the present invention are not substantially colored, and are preferably pale, transparent or white, and preferably white. As having a refractive index of 1.4 to 1.8, for example, minerals such as talc, mica or kaolin clay, oxides such as alumina (aluminum oxide) or silica (silicon oxide), sulfates such as barium sulfate or calcium sulfate, barium carbonate, Carbonates such as calcium carbonate, magnesium carbonate or strontium carbonate, sodium metasilicate or sodium stearate, but aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, carbonic acid, from the viewpoint of electrical reliability It is preferably a material selected from the group consisting of strontium and sodium metasilicate, and barium sulfate is more preferable. Moreover, as commercially available barium sulfate, for example, "BARIFINE" (registered trademark) BF-10, BF-1, BF-20 or BF-40 (above, all manufactured by Sakai Chemical Industry Co., Ltd.) is mentioned. The fine particles having a refractive index of 1.4 to 1.8 of the present invention preferably have a whiteness of 30% or more and 50% or more measured by a method in accordance with JIS P8148 (2001). As much as possible, sufficient pressure is applied to the fine particles to fill the measuring container for measurement, and all of the fine particles shown in this section have a whiteness of 30% or more.

The shape of the fine particles is not particularly limited, and examples thereof include a spherical shape, an ellipsoid shape, a needle shape, a polygonal shape, a star shape, a shape having irregularities or pores on the surface, or a hollow shape.

The particle size of the fine particles is preferably 1 µm or less, preferably 5 to 500 nm, more preferably 10 to 100 nm. If the particle size of the fine particles is too small, dispersion stabilization tends to be difficult. On the other hand, if it is too large, the scattering of light tends to increase and the reflectance tends to increase. Here, the particle size of the fine particles refers to the primary particle size of the fine particles. The primary particle size of the fine particles can be calculated by observing the primary particle diameters of 100 randomly selected fine particles with an electron microscope and obtaining the average value thereof. When the shape is not spherical, the average value of the maximum width and the minimum width observed by an electron microscope for one particle can be calculated by calculating the average value of 100 primary particle diameters by calculating the average particle diameter of the particles. It is preferable that the fine particles having the above particle size are contained in at least 90% by mass of the fine particles contained in the low optical density layer.

Examples of the method for producing fine particles include a pulverization method in which a substance such as a mineral as a raw material is pulverized and refined, a chemical method in a gas phase, a liquid phase or a high layer, or a physical method. As a grinding method, a jet method, a hammer method, or a mill method is mentioned, for example. As a chemical method in a gas phase, a chemical vapor deposition method (CVD method), an electric furnace method, a chemical salt method, or a plasma method is mentioned, for example. As a chemical method in a liquid phase, a precipitation method, an alkoxide method, or a hydrothermal method is mentioned, for example. As a chemical method in a solid phase, a crystallization method is mentioned, for example. As a physical method, a spray method, a solution combustion method, or a freeze drying method is mentioned, for example. Especially, the precipitation method is preferable because the particle diameter of the fine particles can be easily controlled.

<Composition of light-shielding layer (A)>

The light-shielding layer (A) in the black matrix substrate of the present invention contains a light-shielding material and fine particles having a refractive index of 1.4 to 1.8, and further preferably contains a resin.

Examples of the light blocking material include black organic pigments, mixed organic pigments, and inorganic pigments. Examples of the black organic pigment include carbon black, resin-coated carbon black, perylene black, and aniline black. Examples of the mixed organic pigment include those obtained by mixing the pigments such as red, blue, green, purple, yellow, magenta, or cyan, and similarly blackened. As an inorganic pigment, graphite is mentioned, for example. Other examples include metal fine particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver. In addition, oxides, complex oxides, sulfides, nitrides and carbides of the metals shown above can be mentioned. Preference is given to at least one selected from titanium oxynitride, in which titanium oxide is nitrogen-reduced, that is, titanium black, titanium nitride, titanium carbide and carbon black. Especially, titanium oxynitride is more preferable.

Titanium oxynitride refers to a compound represented by TiN _x O _y (0 <x <2.0, 0.1 <y <2.0), but x / y is preferably 0.1 to 10 because the blackness decreases when the content of oxygen is high. And more preferably 1 to 3.

The particle diameter of the light-shielding material is preferably 10 to 300 nm, and more preferably 30 to 100 nm. Here, the particle diameter of the light-shielding material refers to the primary particle diameter of the light-shielding material. The primary particle diameter of the light-shielding material can be calculated by the same method as that of fine particles. If the particle diameter of the light-shielding material is too large, fine pattern processing tends to be difficult. On the other hand, if the particle diameter is too small, the particles of the light-shielding material tend to aggregate and the reflectance tends to be high.

The ratio of the light-shielding material to the light-shielding layer (A) is preferably 5% by mass or more and 10% by mass or more. In addition, the proportion is preferably 80% by mass or less and 50% by mass or less. When the proportion of the light-shielding material is small, it is difficult to obtain a sufficient optical density. On the other hand, when the proportion of the light-shielding material is large, patterning of the light-shielding layer (A) may be difficult.

The proportion of the fine particles in the light-shielding layer (A) is preferably 1% by mass or more, and more preferably 10% by mass or more. Moreover, the proportion is preferably 60% by mass or less, and more preferably 50% by mass or less. If the proportion of fine particles is too small, the effect of the present invention may be insufficient. On the other hand, when the proportion of fine particles is too large, patterning tends to be difficult.

The proportion of the resin that can contain the light-shielding layer (A) is preferably 10% by mass or more, and more preferably 30% by mass or more. Moreover, the proportion is preferably 90% by mass or less, and more preferably 70% by mass or less.

The resin preferably has a refractive index at a wavelength of 589 nm of 1.4 to 1.8, more preferably 1.5 to 1.7. For example, epoxy resin, acrylic resin, siloxane polymer-based resin, or polyimide resin is mentioned. Among these resins, an acrylic resin or a polyimide resin is preferable, and a polyimide resin is more preferable because the heat resistance of the coating film is high. Here, the polyimide resin includes, in addition to the polyimide resin having a completely acyclic ring structure, polyamic acid, which is a precursor of the polyimide resin, and a polyimide resin partially closed by polyamic acid.

The polyimide resin is formed by heating and closing imidized polyamic acid as a precursor. The polyamic acid is generally obtained by addition polymerization of a compound having an acid anhydride group and a diamine compound at 40 to 100 ° C. It has a repeating structural unit represented by the following general formula (1). The polyimide resin in which the polyamic acid is partially closed is an amic acid structure represented by the following general formula (2), a structure represented by the following general formula (3) in which the amic acid structure is partially imide closed, and an amic acid structure. It has an imide structure represented by the following general formula (4) formed by imide closure.

(1)

(One)

(2)

(2)

(3)

(3)

(4)

(4)

In the general formulas (1) to (4), R ¹ represents a trivalent or tetravalent organic group having ² to 22 carbon atoms, R ² represents a divalent organic group having 1 to 22 carbon atoms, and n is 1 or 2 Represents an integer.

An aromatic diamine compound is preferable as the diamine compound used to obtain polyamic acid in order to increase the heat resistance and insulation properties of the polyimide resin, and an acid dianhydride is preferable as the compound having an acid anhydride group.

Examples of the aromatic diamine compound include paraphenylenediamine, metaphenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 4,4 '-Diaminodiphenylsulfide, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (trifluoromethyl) benzidine, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 2, 4'-diaminodiphenylamine, 4,4'-diaminodibenzylamine, 2,2'-diaminodibenzylamine, 3,4'-diaminodibenzylamine, 3,3'-diaminodi Benzylamine, N, N'-bis- (4-amino-3-methylphenyl) ethylenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenz Ah Reed, 4,3'-diaminobenzanilide, 2,4'-diaminobenzanilide, N, N'-p-phenylenebis-p-aminobenzamide, N, N'-p-phenylenebis- m-aminobenzamide, N, N'-m-phenylenebis-p-aminobenzamide, N, N'-m-phenylenebis-m-aminobenzamide, N, N'-dimethyl-N, N '-p-phenylenebis-p-aminobenzamide, N, N'-dimethyl-N, N'-p-phenylenebis-m-aminobenzamide, N, N'-diphenyl-N, N' -p-phenylenebis-p-aminobenzamide or N, N'-diphenyl-N, N'-p-phenylenebis-m-aminobenzamide, but paraphenylenediamine, metaphenylene Diamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4 ' -Diaminodiphenylsulfone, 9,9'-bis (4-aminophenyl) fluorene or 4,4'-diaminobenzanilide is preferred.

As aromatic tetracarboxylic acid, for example, 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4, 9,10-Perylenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride Water, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-paraterphenyltetracarboxylic dianhydride or 3,3', 4,4'-metater Phenyltetracarboxylic dianhydride and the like, but 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-benzophenonetetracarboxylic dianhydride or pyromellitic dianhydride is preferred. Further, when the same fluorine-based tetracarboxylic dianhydride as 4,4'-hexafluoroisopropylidene) diphthalic dianhydride is used, polyimide having good transparency in a short wavelength region can be obtained.

In addition polymerization of a compound having an acid anhydride group and a diamine compound for obtaining a polyamic acid, an acid anhydride such as maleic anhydride or phthalic anhydride may be added as a terminal sealant if necessary. Moreover, in order to improve the adhesiveness with inorganic substances such as a glass plate or a silicon wafer, an acid anhydride having a silicon atom or a diamine compound having a silicon atom may be used. As a diamine having a silicon atom, a siloxane diamine compound such as bis-3- (aminopropyl) tetramethyl siloxane is preferable. The proportion of diamines having silicon atoms in the total diamine compound is preferably 1 to 20 mol%. When there are few siloxane diamine compounds, the effect of improving adhesiveness cannot be obtained. On the other hand, if it is too large, the heat resistance of the film tends to decrease. In addition, the pattern formation of the light-shielding layer may be developed in an alkaline solution, but if the amount is too large, excessively high adhesiveness may occur, resulting in a problem of residual film during alkali development.

As a compound having an acid anhydride group for obtaining a polyamic acid and a diamine compound, an alicyclic acid dianhydride or an alicyclic diamine may be used. Examples of the alicyclic acid dianhydride or alicyclic diamine include 1,2,4,5-cyclohexanetetracarboxylic dianhydride and bicyclo [2.2.2] octo-7-ene-2,3,5 , 6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptan-2-end-3-end-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, Bicyclo [2.2.1] heptan-2-exo-3-exo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptan-2 , 3,5,6-tetracarboxylic dianhydride or decahydro-dimethanonaphthalenetetracarboxylic dianhydride or bis [2- (3-aminopropoxy) ethyl] ether, 1,4-butanediol-bis (3-aminopropyl) ether, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis (2-aminoethoxy) Ethane, 1,2-bis (3-aminopropoxy) ethane, triethylene glycol-bis (3-aminopropyl) ether, polyethylene glycol-bis (3-aminopropyl) ether , 3,9-bis (3-aminopropyl) -2,4,8,10-spiro-5,5-undecane, or 1,4-butanediol - may be a bis (3-aminopropyl) ether.

The light-blocking layer (A) may contain an adhesion improver, a polymer dispersant, or a surfactant as other additives. As an adhesion improving agent, a silane coupling agent or a titanium coupling agent is mentioned, for example. It is preferable to add 0.2-20 mass% of adhesive improving agent with respect to resin, such as polyimide resin and acrylic resin. Examples of the polymer dispersant include polyethyleneimine-based polymer dispersants, polyurethane-based polymer dispersants, and polyarylamine-based polymer dispersants. The polymer dispersant is generally added in an amount of 1 to 40% by mass relative to the light-shielding material. As the surfactant, for example, anionic surfactants such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate or lauryl trimethyl ammochloride, lauryldimethylamine oxide or la Main skeletons include amphoteric surfactants such as urylcarboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate, polydimethylsiloxane, etc. And silicone-based surfactants or fluorine-based surfactants. The surfactant is generally added in an amount of 0.001 to 10% by mass relative to the pigment, but is preferably added in an amount of 0.01 to 1% by mass. When the surfactant is small, the coating property, the smoothness of the colored film, or the effect of preventing Benard cells may be insufficient. On the other hand, if there are too many surfactants, the coating film properties may be poor. The above various additives are included in the composition at the time of providing the light-shielding layer (A), but after that, they may be chemically reacted with the resin by heating or light irradiation to be blown into the chemical structure of the resin.

<< Light-shielding layer (B) >>

<Composition of light-blocking layer (B)>

The light-shielding layer (B) in the black matrix substrate of the present invention contains a light-shielding material, and more preferably a resin.

The light-shielding material contained in the light-shielding layer (B) may be the same as the light-shielding layer (A), but one having at least OD / T selected from carbon black, titanium oxynitride, titanium nitride, and titanium carbide is preferred. And, titanium nitride or titanium nitride is more preferable. Here, the titanium nitride refers to a material containing titanium nitride as a main component and titanium oxide (TiO ₂ ), low-order titanium oxide (TinO _{2n -1} (1≤n≤20)) or titanium oxynitride as a sub-component. The titanium nitride particles contain an oxygen atom, but in order to obtain a higher OD / T, the less oxygen atom is preferred, the oxygen atom content is more preferably 12% by mass or less, and more preferably 8% by mass or less.

As the synthesis of titanium nitride particles, for example, a gas phase reaction method such as an electric furnace method or a thermal plasma method can be used. Among them, the thermal plasma method is preferable because of the low mixing of impurities, the particle diameter is easy to prepare, and the productivity is high. As a method for generating a thermal plasma, for example, direct current arc discharge, multi-layer arc discharge, high-frequency (RF) plasma or hybrid plasma can be mentioned. Among them, high-frequency plasma is preferable because there is little mixing of impurities from the electrode.

The particle diameter of the light-shielding material is preferably 10 to 300 nm, and more preferably 30 to 100 nm. Here, the particle diameter of the light-shielding material refers to the primary particle diameter of the light-shielding material. The primary particle diameter of the light-shielding material can be calculated by the same method as that of fine particles. When the particle diameter of the light-shielding material exceeds 300 nm, fine pattern processing may be difficult. On the other hand, if it is less than 10 nm, aggregation of particles tends to occur and the reflectance tends to increase.

The ratio of the light-shielding material to the light-shielding layer (B) is preferably 10% by mass or more, and more preferably 40% by mass or more. Moreover, the proportion is preferably 90% by mass or less, and more preferably 80% by mass. When the proportion of the light-shielding material is small, it is difficult to obtain a sufficient optical density. On the other hand, if too many, patterning becomes difficult.

The proportion of the resin that can contain the light-blocking layer (B) is preferably 10% by mass or more, and more preferably 20% by mass or more. Moreover, the proportion is preferably 90% by mass or less, and more preferably 60% by mass or less.

As the resin which can contain the light-shielding layer (B), the same thing as the resin contained in the light-shielding layer (A) can be mentioned, but among them, an acrylic resin is preferable.

As the acrylic resin, an acrylic polymer having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used.

Examples of the unsaturated carboxylic acid used as a raw material for the copolymer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, or vinyl acetic acid. Examples of the ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, and n-acrylate Butyl, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, And unsaturated carboxylic acid alkyl esters such as n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, or benzyl methacrylate. Moreover, aromatic vinyl compounds, such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, or alpha-methylstyrene, are mentioned as another ethylenically unsaturated compound. Others include unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate or glycidyl methacrylate, vinyl carboxylates such as vinyl acetate or vinyl propionate Esters and the like. Further, the oligomer or polymer having an unsaturated group at the terminal can also be grafted by copolymerizing it as a macromonomer. For example, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloracrylonitrile, 1,3-butadiene Alternatively, an aliphatic conjugated diene such as isoprene, polystyrene, polymethylacrylate, polymethylmethacrylate, polybutylacrylate or polybutylmethacrylate having an acryloyl group or methacryloyl group at each terminal may be used. Of these copolymer components, copolymers of 2 to 4 components of monomers selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene are preferred. Do. It is common to perform development operation when pattern-processing resin BM. In order to make the dissolution rate for the alkali developer frequently used appropriate, the weight average molecular weight (Mw) (tetrahydrofuran as a carrier was measured by gel permeation chromatography at a temperature of 23 ° C. and converted using a calibration curve with standard polystyrene). It is more preferable that the acid value is 20 to 100,000 and the acid value is 70 to 150 (mgKOH / g).

Further, an acrylic resin having an ethylenically unsaturated group in the side chain can be contained in the raw material step of the light-blocking layer (B). By containing this material, the sensitivity in exposure and development in pattern processing of resin BM can be improved. As the ethylenically unsaturated group, an acrylic group or methacryl group is preferable. The acrylic resin having an ethylenically unsaturated group in the side chain can be obtained by adding an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic resin having a carboxyl group.

Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include commercially available acrylic resin CYCLOMER (registered trademark) P (manufactured by Daicel Corporation) or an alkali-soluble cardo resin, but are soluble in an ester solvent or an alkali developer. In order to make it suitable, it is preferable that the weight average molecular weight (Mw) is 20 to 100,000 and the acid value is 70 to 150 (mgKOH / g).

The polyfunctional acrylic monomer or its reactant may be further contained in the raw material of the light-blocking layer (B). The light shielding layer is pattern-processed later, but the processing is generally performed in the order of pattern exposure and development. The compound is polymerized and crosslinked by exposure, and insoluble in the developer. Examples of the polyfunctional acrylic monomer include a polyfunctional acrylic monomer or oligomer. Examples of the polyfunctional acrylic monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, and adipic acid 1,6- Hexanediol (meth) acrylic acid ester, phthalic anhydride propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxydi (meth) acrylate, alkyd modified (meth) acrylate, flu Orendiacrylate-based oligomer, tripropylene glycol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethyrolpropane tri ( Meth) acrylate, pentaerythritol tri (meth) acrylate, triacrylic formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy -2-hydroxypropoxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) Phenyl] ether, 4,4'-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypro) Foxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- ( 3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanolfluorenediacrylate, bisphenoxyethanolfluorenedimethacrylate, biscresolfluorenediacrylate and biscresol And fluorene methacrylate.

These polyfunctional monomers or oligomers can be appropriately selected and combined, compounds having three or more functional groups are preferable, compounds having five or more functional groups are more preferable, and dipentaerythritol hexa (meth) acrylate or dipenta Erythritol penta (meth) acrylate is more preferred.

The light-shielding layer (B) is preferably a combination of a polyfunctional acrylic monomer that cures sensitively even with a small amount of ultraviolet light, because the light-shielding material contained tends to absorb not only the visible light region but also the ultraviolet light effective for cross-linking light. In addition to dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate, it is preferable to use (meth) acrylate having a highly water-repellent fluorene ring containing many aromatic rings in the molecule. . It is preferable to use 90-40 mass parts of (meth) acrylate which has a fluorene ring with respect to 10-60 mass parts of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate.

The light-blocking layer (B) may contain a photopolymerization initiator. For example, benzophenone compounds, acetophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, oxime ester compounds, carbazole compounds, triazine compounds, phosphorus compounds or tita And inorganic photopolymerization initiators such as Nate.

More specifically, for example, benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone , Benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylphenylketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-1-propane, "IRGACURE" 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone), copper OXE01 (1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]), CGI-113 (2- [4-methylbenzyl]- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, t-butylanthraquinone) or CGI-242 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime)) (above, all manufactured by Ciba · Specialty · Chemicals), 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chlor-2- Methyl anth Laquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- ( o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (Trichloromethyl) -s-triazine or "ADEKA" (registered trademark) "OPTOMER" (registered trademark) N-1818 or a carbazole-based compound such as N-1919 (all manufactured by Asahi Denka Kogyo KK); have. The raw material of the light-blocking layer (B) may contain, as other additives, an adhesion improver, a polymer dispersant, or a surfactant. Specifically, the same thing as what is contained in the light-shielding layer (A) can be mentioned.

<< resin BM >>

The thickness of the light-shielding layer (A) and the light-shielding layer (B) in the black matrix substrate of the present invention is preferably 0.3 µm or more and 0.4 µm or more, respectively. Moreover, 1.2 micrometers or less and 1.0 micrometers or less are preferable respectively. Moreover, the film thickness of the whole resin BM in which both layers are combined is preferably 0.5 µm or more, and 1.0 µm or more. Moreover, it is preferable that this film thickness is 2.0 micrometers or less, and also 1.5 micrometers or less. If the overall film thickness is too thin, a suitable optical density may not be obtained. On the other hand, if it is too thick, the contrast may fall due to poor alignment of the liquid crystal.

As the pattern shape of the resin BM formed on the black matrix substrate of the present invention, for example, a shape having a rectangle, a stripe, a square, a polygon, a waveform, or irregularities is mentioned. The width of the pattern is preferably 3 to 30 μm, more preferably 3 to 10 μm, and even more preferably 3 to 6 μm. If the pattern width is too large, the area of the opening of the pixel may be small, resulting in a decrease in luminance. On the other hand, if the pattern width is too small, the pattern may be lost during processing.

The pattern of the light-shielding layer (A) constituting the black matrix substrate of the present invention and the pattern of the light-shielding layer (B) are preferably the same since the luminance is improved by maximizing the opening area of the pixel. Specifically, it is preferable that the pattern shapes of the light-blocking layer A and the light-blocking layer B, such as a rectangle or a stripe, are almost the same. The pattern width need not be exactly the same, but the difference between the pattern width of the light-shielding layer (A) and the pattern width of the light-shielding layer (B) is preferably 3 µm or less, more preferably 1 µm or less, and further 0.5 µm or less. desirable.

The surface resistance value (Ω / □) of the resin BM formed on the black matrix substrate of the present invention is preferably 10 ⁸ (Ω / □) or more, and more preferably 10 ¹⁵ (Ω / □) or more. By forming the resin BM having a large surface resistance value, the insulating property of the color filter substrate is increased, so that the electric field is not disturbed when a voltage is applied, and good liquid crystal orientation is obtained, and as a result, a liquid crystal display device having a good quality display is obtained. Can be.

<< transparent board >>

Examples of the transparent substrate include quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as silicate soda-lime glass, or films or sheets of organic plastics, and preferably have a refractive index of 1.4 to 1.8. And more preferably 1.5 to 1.7. Transparency referred to herein means that the transmittance is 80% or more in all regions of the wavelength of 380 to 700 nm, and is preferably 90% or more.

As a film of organic plastic, polyimide resin is preferable. By using a polyimide resin as a transparent substrate, it is possible to obtain a flexible black matrix substrate and a color filter substrate having excellent heat resistance and dimensional stability.

The film of the polyimide resin can be produced by applying a solution of a polyimide precursor resin such as polyamic acid on a top plate, followed by drying and heating.

First, a polyimide precursor resin composition is applied on a top plate. Examples of the material of the top plate include silicon wafers, ceramics, gallium arsenide, soda-lime glass, or alkali-free glass. Examples of the method for applying the solution of the polyimide precursor resin on the base plate include a slit coating method, a spin coating method, a spray coating method, a roll coating method or a bar coating method, but a spin coating method or a slit coating method. This is preferred. Next, the top plate coated with the solution of the polyimide precursor resin is dried to obtain a polyimide precursor resin composition film. As a method of drying, for example, a method using a hot plate, an oven, an infrared ray, or a vacuum chamber is used. When a hot plate is used, the top plate is dried by heating it on a hot plate or on a jig such as a proxy pin installed on the hot plate. Subsequently, the polyimide precursor resin composition film is heated at 180 to 400 ° C to convert it into a polyimide resin film.

As a method of peeling this polyimide resin film from the top plate, for example, a method of mechanical peeling, a method of immersing in a chemical solution or water such as hydrofluoric acid, or a method of irradiating a laser to the interface between the polyimide resin film and the top plate. Can be lifted. In addition, a black matrix substrate, a liquid crystal display device, or a light emitting device may be manufactured without peeling the polyimide resin film from the top plate, and then the polyimide resin film may be peeled from the top plate, but from the viewpoint of dimensional stability, the color filter substrate. It is preferable to peel off the top plate after preparing the back.

<< Method for forming light-blocking layer (A) and light-blocking layer (B) >>

As a method of forming the light-shielding layer (A) and the light-shielding layer (B) on the transparent substrate of the present invention, for example, the following two methods are exemplified.

1) How to repeat the photolithography process multiple times

A light-blocking layer (A) that is not yet patterned is provided on the transparent substrate, and the layer is patterned. Thereafter, a light shielding layer (B) that is not yet patterned is further provided, and the layer is patterned.

As a method of patterning the light-shielding layer A, a photolithographic method is exemplified. A method is illustrated in which a light-shielding layer (A) is provided using a photosensitive resin composition to expose a pattern and develop to obtain a pattern. As a separate method, a light shielding layer (A) is provided using a non-photosensitive resin composition. A photoresist is provided thereon to expose the pattern and develop to form a pattern of the photoresist. At the same time as the development, the light-blocking layer A can also be patterned by etching the pattern of the photoresist with a developer as a mask. The pattern of the photoresist after development can also be patterned by etching the light-shielding layer (A) with a solvent as a mask. The pattern of the light-shielding layer (B) can also be formed similarly to the patterning method of the light-shielding layer (A) described above.

2) Method of performing photolithography process once

A light shielding layer (A) that is not yet patterned is provided on the transparent substrate, a light shielding layer (B) that is not patterned is further provided, and the light shielding layer (A) and the light shielding layer (B) are formed by a photolithographic method. Pattern. In the photolithographic method, a photoresist is provided on the light-blocking layer (B) to expose the pattern, and at the same time as the photoresist is developed, the light-resisting layer (B) and the light-blocking layer (A) are etched using the photoresist pattern as a mask to etch the pattern. To form. Alternatively, after the pattern of the photoresist is formed, the light-shielding layer (A) and the light-shielding layer (B) may be patterned with a solvent using the pattern of the photoresist as a mask. In addition, as a method of performing separate photolithography once, a light-shielding layer (A) that is not yet patterned is provided on a transparent substrate, and a non-patterned light-shielding layer (B) made of a photosensitive resin composition is further installed, and a photo The light shielding layer (B) is patterned by a lithographic method, and the light shielding layer (A) is patterned with a developer or a solvent. In this case, a photosensitive resin composition may be used for the light-shielding layer (A).

The details of the method of forming the pattern of the light-shielding layer (A) and the light-shielding layer (B) in the black matrix substrate will be described. The light-shielding layer (A) is obtained by applying a resin composition as a raw material to a transparent substrate. As a method of coating the resin composition on the transparent substrate, for example, a spin coater, bar coater, blade coater, roll coater, die coater, and screen printing method are mentioned. Other methods include a method of immersing the transparent substrate in the black resin composition and a method of spraying the black resin composition on the substrate. In order to improve the coatability, the resin composition may further contain a solvent. For example, amides such as esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, N-methyl-2-pyrrolidone, N, N-dimethylacetamide or N, N-dimethylformamide Although a system polar solvent or lactones can be mentioned, in order to increase the dispersion effect of the pigment as a light-shielding material, a mixed solvent containing lactones or lactones as a main component is preferable. Here, the solvent containing lactones as a main component means a solvent having a maximum mass ratio of lactones to all solvents. Moreover, as a lactone, the C3-C12 aliphatic cyclic ester compound is preferable. Examples of lactones include β-propiolactone, γ-butylolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, or ε-caprolactone. Among them, γ-butylolactone is preferred from the viewpoint of solubility of the polyimide precursor. Moreover, as solvents other than lactones, for example, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl Ether, tripropylene glycol monomethyl ether, propylene glycol mono tertiary butyl ether, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol , Methyl carbitol aceto, ethyl carbitol, and ethyl carbitol acetate.

The proportion of the solvent in the black resin composition used for forming the light-shielding layer (A) is preferably 70 to 98% by mass, and more preferably 80 to 95% by mass from the viewpoint of coatability and dryness.

As a manufacturing method of the resin composition used for formation of a light-shielding layer (A), the method of dispersing a light-shielding material and microparticles | fine-particles directly in a resin solution using a disperser is mentioned, for example. Another method is a method of dispersing a light-shielding material and fine particles in water or an organic solvent using a disperser to prepare a dispersion, and then mixing the dispersion and the resin solution. As a method for dispersing the light-shielding material and fine particles, for example, a ball mill, a sand grinder, three roll mills, or a high-speed impact mill can be mentioned. Especially, a bead mill is preferable from a viewpoint of dispersion efficiency and micro-dispersion. Examples of the bead mill include a co-ball mill, a basket mill, a pin mill or a dino mill. As the bead mill beads, titania beads, zirconium oxide beads or zircon beads are preferable, for example. The bead diameter used for dispersion is preferably 0.01 to 5.0 mm, and more preferably 0.03 to 1.0 mm. When the primary particle diameter of the pigment or the secondary particle formed by the aggregation of the primary particles is small, a fine dispersion bead of 0.03 to 0.10 mm is preferable as a bead diameter used for dispersion. In this case, it is preferable to disperse using a bead mill having a separator by a centrifugal separation method capable of separating a fine dispersion bead and a dispersion. On the other hand, in the case of dispersing the light-shielding material or fine particles containing coarse particles having a submicron level, dispersion beads having a bead diameter of 0.10 mm or more are preferable in order to obtain sufficient grinding power. Further, the light blocking material and the fine particles may be dispersed respectively. In this case, in order to prevent agglomeration by solvent shock, it is preferable to use the same solvent.

The coated film obtained by applying the resin composition as described above on a transparent substrate is dried and cured by air drying, heat drying or vacuum drying to form a dry film. In order to suppress drying unevenness or conveyance unevenness, it is preferable that the transparent substrate coated with the black resin composition is dried under reduced pressure in a vacuum dryer equipped with a heating device, and then heated to semi-cured (semi-cure).

Subsequently, in order to form the light-blocking layer (B) on the dry film of the light-blocking layer (A), the black composition for the light-blocking layer (B) is applied and dried so that the OD / T is greater than that of the light-blocking layer (A).

The black composition for forming the light-shielding layer (B) is preferably formed using a photosensitive black resin composition containing a light-shielding material, a resin, a solvent, a polyfunctional acrylic monomer, and a photopolymerization initiator.

As a solvent contained in the photosensitive black resin composition used for forming the light-shielding layer (B), water or an organic solvent can be appropriately selected depending on the dispersion stability of the light-shielding material to be dispersed and the solubility of the resin component to be added. Examples of the organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents and lactone polar solvents. As esters, for example, benzyl acetate (boiling point 214 ° C), ethylbenzoate (boiling point 213 ° C), methylbenzoate (boiling point 200 ° C), diethyl malonate (boiling point 199 ° C), 2-ethylhexyl acetate (boiling point) 199 ° C), 2-butoxyethyl acetate (boiling point 192 ° C), 3-methoxy-3-methyl-butyl acetate (boiling point 188 ° C), diethyl oxalate (boiling point 185 ° C), ethyl acetoacetate (boiling point 181 ° C) , Cyclohexyl acetate (boiling point 174 ° C), 3-methoxy-butyl acetate (boiling point 173 ° C), acetoacetic acid methyl (boiling point 172 ° C), ethyl-3-ethoxypropionate (boiling point 170 ° C), 2-ethyl Butyl acetate (boiling point 162 ° C), isopropylpropionate (boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), pentyl acetate (boiling point 150) ℃) or propylene glycol monomethyl ether acetate (boiling point 146 ° C), etc. Can.

In addition, as solvents other than the above, for example, ethylene glycol monomethyl ether (boiling point 124 ° C), ethylene glycol monoethyl ether (boiling point 135 ° C), propylene glycol monoethyl ether (boiling point 133 ° C), diethylene glycol monomethyl ether ( Boiling point 193 ° C), monoethyl ether (boiling point 135 ° C), methylcarbitol (boiling point 194 ° C), ethyl carbitol (202 ° C), propylene glycol monomethyl ether (boiling point 120 ° C), propylene glycol monoethyl ether (boiling point 133) ℃), (poly) alkylene glycol ether solvents such as propylene glycol tertiary butyl ether (boiling point 153 ° C) or dipropylene glycol monomethyl ether (boiling point 188 ° C), ethyl acetate (77 ° C boiling point), butyl acetate (boiling point) 126 ° C) or aliphatic esters such as isopentyl acetate (boiling point 142 ° C), butanol (boiling point 118 ° C), 3-methyl-2-butanol (boiling point 112 ° C) or 3-methyl-3-methoxy butanol (boiling point 174) ℃) aliphatic alcohols such as cyclopentanone Or ketones such as cyclohexanone, xylene (boiling point 144 ° C), ethylbenzene (boiling point 136 ° C), or solvent naphtha (petroleum fraction: boiling point 165 to 178 ° C).

In addition, since the coating by the die coating device has become mainstream with the enlargement of the transparent substrate, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C to 200 ° C is preferable in order to realize proper volatility and dryness. .

The method similar to the light-shielding layer (A) is mentioned as a manufacturing method of the photosensitive resin composition which can be used for formation of a light-shielding layer (B).

As described above, the resin composition for forming the light-shielding layer (A) is applied and dried, and then the photosensitive resin composition for forming the light-shielding layer (B) is applied and dried, and then ultraviolet light is emitted from the exposure apparatus through a mask. It irradiates and develops, for example with an alkaline developing solution. As the alkaline developer, an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of alkali metal hydroxide can be used. Surfactants such as nonionic surfactants can be added to the developer, for example, 0.01 to 1% by mass.

The obtained pattern then becomes a patterned resin BM by heat treatment. The heat treatment of the pattern in the lamination state is preferably carried out continuously or stepwise at 150 to 300 ° C for 0.25 to 5 hours in air, nitrogen or vacuum, for example. Further, the temperature of the heat treatment is more preferably 180 to 250 ° C.

In addition, the pattern formation method of the resin BM can be applied even when the light-shielding layer (A) does not contain fine particles having a refractive index of 1.4 to 1.8.

Next, a preferable shape of the resin BM will be described. 1 is a schematic view showing some embodiments of a black matrix substrate of the present invention. The resin BM 11 comprising the light-blocking layer A having a small OD / T and the light-blocking layer B having a large OD / T is patterned on the transparent substrate 10. The resin BM formed on the black matrix substrate of the present invention needs to have layers in order, as shown in Figs. 1 (a) to (e), but as shown in Fig. 1 (a), as shown in Fig. 1 (b). The acid pattern, the inverse pattern as shown in Fig. 1 (c), the pattern of the light shielding layer B as shown in Fig. 1 (d) is smaller than the light shielding layer A, and the light shielding layer as shown in Fig. 1 (e) ( The pattern of B) may be any one disposed larger than the light-shielding layer (A). Among them, in order to improve the aperture ratio of the pixel by thinning the line width of the resin BM, the light blocking layer (A) 21 and the light blocking layer (B) 22 are shown as shown in FIGS. 1 (a) to (c). It is preferable to have a width of about the same degree, and it is more preferable that they are stacked in an acid form as shown in Fig. 1 (b). In addition, as shown in FIG. 2, the line width of the place where the light-shielding layer (A) 21 is in contact with the transparent substrate 10 is L1, the boundary portion between the light-shielding layer (A) 21 and the light-blocking layer (B) 22 When the line width of L2 and the line width of the government of the light-blocking layer (B) 22 are L3, it is preferable to satisfy the relationship of L1> L2> L3 in order to improve visibility. Further, the difference between L1 and L3 is preferably 3 µm or less, more preferably 1 µm or less, and even more preferably 0.5 µm or less.

<< Use of black matrix substrate >>

The black matrix substrate of the present invention can be used for electronic materials and various displays. Making light-shielding images such as barrier ribs, dielectric patterns, electrode (conductor circuit) patterns, or wiring patterns of electronic components utilizing the characteristics of high optical density and low light reflection of the black matrix substrate of the present invention. Can be used for Among them, in order to improve the display characteristics of a color filter used in a color liquid crystal display device or the like, resin BM is preferable as a black matrix substrate provided on a gap portion and a peripheral portion of a colored pattern, and on the external light side of a TFT.

<Color filter>

In the color filter substrate disclosed by the present invention, colored pixels such as red, green, and blue are formed in a non-existent portion of a resin BM pattern as a light-shielding layer using the black matrix substrate of the present invention.

As a method of manufacturing the color filter substrate of the present invention, for example, after forming a resin BM on a transparent substrate, a method of forming a pixel having color selectivity of red (R), green (G) or blue (B) is mentioned. Can be. If necessary, an overcoat film may be formed on this. Examples of the overcoat film include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a silicon-containing polyimide film, and a polyimide siloxane film. A transparent conductive film may be further formed on the overcoat film. As a transparent conductive film, oxide thin film, such as ITO, is mentioned, for example. As a method for producing an ITO film having a film thickness of about 0.1 µm, for example, sputtering or vacuum deposition can be used. As the material of the pixel, for example, an inorganic film whose film thickness is controlled so as to transmit only arbitrary light, or a colored resin film in which dyeing, dye dispersion or pigment dispersion is carried out is exemplified.

It is preferable that the pigment dispersed in the pixel of the color filter substrate of the present invention is excellent in light resistance, heat resistance and chemical resistance.

As a red pigment, for example, Pigment Red (hereinafter "PR") 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR190, PR192, PR209, PR215, PR216 , PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240 and PR254.

Examples of the orange pigment include pigment orange (hereinafter referred to as "PO") 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65 and PO71. .

As the yellow pigment, for example, Pigment Yellow (hereinafter referred to as "PY") PY12, PY13, PY14, PY17, PY20, PY24, PY83, PY86, PY93, PY94, PY95, PY109, PY110, PY117, PY125, PY129 , PY137, PY138, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY173, PY180 or PY185.

Examples of the purple pigment include pigment violet (hereinafter referred to as "PV") 19, PV23, PV29, PV30, PV32, PV36, PV37, PV38, PV40 and PV50.

Examples of the blue pigment include Pigment Blue (hereinafter referred to as "PB") 15, PB15: 3, PB15: 4, PB15: 6, PB22, PB60, PB64 and PB80.

Examples of the green pigment include pigment green (hereinafter referred to as "PG") 7, PG10, PG36, and PG58.

These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment or basic treatment, if necessary. Further, a pigment derivative may be added as a dispersant.

When the pixel of the color filter substrate of the present invention is a colored resin film with pigment dispersion, acrylic resin, polyvinyl alcohol, polyamide, and polyimide are examples of the binder resin used for the formation, but heat resistance and chemical resistance From the viewpoint of, polyimide is preferred.

The color filter substrate of the present invention may form a fixed spacer. The fixed spacer is fixed to a specific place on the color filter substrate and refers to a contact with the counter substrate when a liquid crystal display device is manufactured. Accordingly, a constant gap is maintained between the opposing substrates, and the liquid crystal compound is filled between the gaps. By forming the fixed spacer, the step of spraying the spherical spacer in the manufacturing process of the liquid crystal display device or the step of kneading the rod-shaped spacer in the sealant can be omitted.

<Liquid crystal display device, light emitting device>

The liquid crystal display device of the present invention has the color filter substrate, a liquid crystal compound, and a counter substrate in order.

In addition, the light emitting device of the present invention is characterized by bonding the color filter substrate of the present invention and a light emitting element.

An organic EL element is preferable as the light emitting element. The light emitting device of the present invention utilizes the feature that the black matrix substrate has high OD and low reflection to effectively shield the extra light from the light emitting element in the black display, while suppressing reflection of external light and obtaining a high contrast display. have.

3 is a schematic cross-sectional view showing an embodiment of a light emitting device.

The light emitting device shown in FIG. 3 is configured by bonding the color filter substrate 20 and the organic EL element 40 as a light emitting element with the sealing agent 34.

The color filter substrate 20 is composed of a black matrix substrate manufactured by the manufacturing method of the present invention, red, green or blue pixels 23 to 25 formed in the openings, and an overcoat layer 26. Here, the black matrix substrate provided in the color filter substrate 20 is composed of a substrate 10 and a resin BM 11 in which the light-blocking layers (A) 21 and the light-blocking layers (B) 22 are stacked.

The organic EL element 40 includes a transparent electrode 28, an organic electric luminescence layer (hereinafter referred to as "organic EL layer") 29, a back electrode layer 30, an insulating film 31, and a substrate. It consists of (32) and an extraction electrode (33) connected to an external power supply. Here, the organic EL layer is composed of a hole transport layer, a light emitting layer, and an electron transport layer.

In FIG. 3, the air gap is formed between the color filter substrate 20 and the organic EL element 40, but a resin or a drying agent may be present as necessary.

Examples of the material of the substrate 32 constituting the organic EL element 40 include transparent materials such as glass, film and plastic, and opaque materials such as aluminum, chromium, stainless steel or ceramics.

The insulating film 31 prevents energization of the transparent electrode 28 and the back electrode layer 30. Examples of the material of the insulating film 31 include polyimide resin, acrylic resin, epoxy resin, and silicone resin, and can be formed by a photolithographic method by using a photosensitive material.

The back electrode layer 30 is positioned between the substrate 32 and the organic EL layer 29, and is a mechanism in which the organic EL layer emits light by applying a voltage between the transparent electrodes 28. Examples of the material of the back electrode layer include magnesium, aluminum, indium, lithium, silver or aluminum oxide. The thickness of the back electrode layer is usually 0.01 to 1 µm, and for example, it can be formed by patterning by a photolithographic method after forming a metal thin film by vapor deposition or sputtering.

It is preferable that the light of the organic EL layer 29 is white light. A light emitting device having a desired color reproduction range can be realized by appropriately changing the color tone of the pixels 23 to 25 of the color filter substrate 20 in accordance with the wavelength distribution of the white light.

Examples of the material of the light emitting layer include cyclopentamine, tetraphenylbutadiene, triphenylamine, oxadiazole, pyrazoloquinoline, distyrylbenzene, distyrylarylene, silol, thiophene, pyridine, perinone, perylene, oligo And organic compounds having a skeleton such as thiophene and trifumanylamine, and dye-based materials such as oxadiazole dimer and pyrazoline dimer. Further, aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, and europium complex are exemplified. Metal complexes such as metal complexes having rare earth metals such as Al, Zn, Be, Tb, Eu or Dy in the central metal, and oxadiazole, thiadiazole, phenylpyridine, phenylbenzoimidazole or quinoline structures in the ligand And system materials. And polymer materials such as polyfluorene derivatives and polyvinylcarbazole derivatives, such as polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, and polyacetylene derivatives. The film thickness of the light emitting layer is usually 0.05 to 5 µm, and can be formed, for example, by a vapor deposition method, a spin coating method, a printing method or an inkjet method.

In order for the transparent electrode 28 to transmit the light emitted from the organic EL layer 29, the transmittance is preferably 80 to 99%, and more preferably 90 to 99%. As the material of the transparent electrode, for example, ITO, indium oxide, zinc oxide, or cuprous oxide can be mentioned. The thickness of the transparent electrode is usually 0.1 to 1 µm, and it can be formed by patterning by a photolithographic method after forming a thin film of metal oxide by vapor deposition or sputtering.

As the material of the lead-out electrode 33, silver, aluminum, gold, chromium, nickel or molybdenum is mentioned, for example.

Moreover, a flexible light emitting device can be obtained by bonding a flexible color filter substrate using a polyimide resin film as a substrate and a light emitting element. In addition, a flexible organic EL display can be manufactured by bonding the flexible color filter substrate and an organic EL element as a light emitting element.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.

<Evaluation method>

[Refractive index of particulates]

The refractive index was obtained by the Beckett method. Thirty samples of the same substance of the target fine particles were prepared, the refractive index was measured one by one, and the refractive index was calculated by their average value.

[Optical density (OD value)]

A light shielding layer having a predetermined film thickness is formed on an alkali-free glass having a thickness of 0.7 mm, and the intensity of each incident light and transmitted light is measured using a microscopic spectroscopy (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.) to obtain the following formula (7) ), And the average value of the values obtained in 5 nm increments in the wavelength range of 380 to 700 nm was obtained.

OD value = log ₁₀ (I ₀ /I)...(7)

I ₀ : incident light intensity

I: transmitted light intensity.

[Reflective chromaticity]

Resin BM having a predetermined film thickness was formed on an alkali-free glass having a thickness of 0.7 mm, and absolute reflection measurement at an incident angle of 5 ° from the glass surface was measured using an ultraviolet visible spectrophotometer (UV-2450; manufactured by Shimadzu Corporation). . From the obtained spectrum, chromaticity values (a *, b *) at the D65 light source calculated by the CIE L * a * b * colorimeter and Y (reflectance) at the D65 light source calculated by the CIE XYZ colorimeter are calculated, hereinafter The reflection chromaticity was judged based on the judgment criteria of.

A: Reflectance is 4.2 or more and less than 4.7, and a * and b * are 1.0 or less

B: Reflectance is 4.2 or more and less than 4.7, and a * and b * are more than 1.0 and less than 2.0

C: Reflectance is 4.2 or more and less than 4.7, and a * or b * is more than 2.0

D: Reflectance is 4.7 or more and less than 5.2, and a * and b * are 1.0 or less

E: Reflectance is 4.7 or more and less than 5.2, and a * and b * are more than 1.0 and less than 2.0

F: Reflectance is 4.7 or more and less than 5.2, and a * or b * is more than 2.0

G: The reflectance is 5.2 or more.

[Surface resistance value]

Using HIRESTA UP MCP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the surface resistance value (Ω / □) was measured at an applied voltage of 10 V, and insulation was determined based on the following criteria.

Excellent: more than the measurement limit (10 ¹⁵ Ω / □ or more) and very high insulation

Good: 10 ⁸ Ω / □ or more and less than 10 ¹⁵ Ω / □ and sufficient insulation

Poor: less than 10 ⁸ Ω / □ and insufficient insulation.

[Particle diameter]

The primary particle diameter of the fine particles was calculated by observing the primary particle diameters of 100 randomly selected fine particles with an electron microscope and obtaining the average value thereof.

<Production Example>

(Synthesis of polyamic acid A-1)

4,4'-diaminophenyl ether (0.30 mol equivalent), paraphenylenediamine (0.65 mol equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 mol equivalent), 850 g and N of γ-butylolactone -850 g of methyl-2-pyrrolidone was added, and 3,3 ', 4,4'-oxydiphthalylcarboxylic acid dianhydride (0.9975 mol equivalent) was added to react at 80 ° C for 3 hours. Further, maleic anhydride (0.02 mol equivalent) was added and reacted at 80 ° C for 1 hour to obtain a polyamic acid A-1 (polymer concentration: 20% by mass) solution.

(Synthesis of polyamic acid A-2)

4,4'-diaminophenyl ether (0.95 mol equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 mol equivalent) and 1700 g (100%) of γ-butylolactone were added, and pyromellitic dianhydride Water (0.49 mol equivalent) and benzophenone tetracarboxylic dianhydride (0.50 mol equivalent) were added and reacted at 80 ° C for 3 hours. Further, maleic anhydride (0.02 mol equivalent) was added, and further reacted at 80 ° C. for 1 hour to obtain a polyamic acid A-2 (polymer concentration: 20% by mass) solution.

(Synthesis of acrylic polymer (P-1))

100 g of isopropyl alcohol was added to a 1000 cc four-necked flask, and this was maintained at 80 ° C. in an oil bath, while nitrogen sealing and stirring were performed, methyl methacrylate 30 g, styrene 40 g, methacrylic acid 30 g and N, N-azobis A mixed solution of 2 g of isobutylonitrile was added dropwise over 30 minutes in a dropping funnel. Thereafter, after the reaction was continued for 4 hours, 1 g of hydroquinone monomethyl ether was added, and then returned to room temperature to complete polymerization. As a result, a solution containing methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) was obtained. Further, after adding 100 g of isopropyl alcohol to the solution, 40 g of methacrylic acid glycidyl and 3 g of triethylbenzylammonium chloride were added and reacted for 3 hours while maintaining this at 75 ° C., and reprecipitation, filtration, and drying with purified water were performed. By doing so, the weight average molecular weight (Mw, tetrahydrofuran as a carrier was measured by gel permeation chromatography at a temperature of 23 ° C. and converted using a calibration curve with standard polystyrene) 40,000, an acrylic polymer having an acid value of 110 (mgKOH / g) ( P-1) powder was obtained. Here, the reaction rate of glycidyl methacrylate was 70% as determined from the change in the polymer acid value before and after the reaction, and the addition amount was 0.73 equivalents.

(Production of light-shielding material dispersion Bk1)

As a thermal plasma method, 4.0 kg of titanium dioxide powder having an average primary particle size of 40 nm was introduced into the reaction furnace, and then ammonia gas was flowed at a linear velocity of 3 cm / sec to react at a temperature of 750 ° C. for 6 hours, followed by oxynitridation. 3.2 kg of titanium (particle size: 40 nm, titanium content: 70.6 mass%, nitrogen content: 18.8 mass%, oxygen content: 8.64 mass%) was obtained. Titanium oxynitride (96 g), polyamic acid solution A-1 (120 g), γ-butylolactone (114 g), N-methyl-2 pyrrolidone (538 g) and 3 methyl-3 methoxybutyl acetate (132 g) Into the tank, stirred for 1 hour with a homomixer (manufactured by Primix Corporation), and ultra apex mill (Kotobuki Industies Co., Ltd.) equipped with a centrifugal separator with 70% filling of 0.05 mmφ zirconium oxide beads (YTZ ball; manufactured by Nikkato Corporation) , Ltd.) to perform dispersion for 2 hours at a rotation speed of 8 m / s, to obtain a light-blocking material dispersion Bk1 having a solid content concentration of 12 mass% and a pigment / resin (mass ratio) = 80/20.

(Production of light-shielding material dispersion Bk2)

Preparation of light blocking material dispersion Bk1 except that titanium nitride particles (manufactured by Wako Pure Chemical Industries, Ltd .; particle diameter: 50 nm, titanium content: 74.3 mass%, nitrogen content: 20.3 mass%, oxygen content: 2.94 mass%) were used as the pigment. Similarly, a light-shielding material dispersion Bk2 was obtained.

(Production of light-shielding material dispersion Bk3)

Light-shielding material dispersion liquid Bk3 was obtained similarly to preparation of light-shielding material dispersion liquid Bk1 except that carbon black (MA100; manufactured by Mitsubishi Chemical Corporation; particle size: 24 nm) was used as a pigment.

(Production of light-shielding material dispersion Bk4)

Titanium nitride particles (manufactured by Wako Pure Chemical Industries, Ltd .; particle size: 50 nm, titanium content: 74.3 mass%, nitrogen content: 20.3 mass%, oxygen content: 2.94 mass%) (200 g), acrylic polymer (P-1) Centrifugation in which 70% by mass of 3-methyl-3-methoxybutanol solution (100 g) and propylene glycol tertiary butyl ether (700 g) were added to the tank, stirred with a homomixer for 1 hour, and then filled with 0.05 mmφ zirconium oxide beads 70%. The dispersion was performed for 2 hours at a rotational speed of 8 m / s using an ultra apex mill equipped with a separator, thereby obtaining a light-blocking material dispersion Bk4 having a solid content concentration of 24.5 mass% and a pigment / resin (mass ratio) = 82/18.

(Preparation of white particulate dispersion WD1)

Silica as white fine particles ("AEROSIL" (registered trademark) OX50; manufactured by Nippon Aerosil Co., Ltd; particle size: 40 nm, refractive index: 1.45) (96 g), polyamic acid solution A-1 (120 g), γ-butylolactone ( 114g), N-methyl-2pyrrolidone (538g) and 3methyl-3methoxybutylacetate (132g) were put into a tank, stirred for 1 hour with a homomixer, and centrifuged with 70% 0.05mmφ zirconium oxide beads Dispersion was performed for 2 hours at a rotational speed of 8 m / s using an ultra apex mill equipped with a separator to obtain a white particulate dispersion WD1 having a solid content concentration of 12% by mass and a pigment / resin (mass ratio) = 80/20.

(Preparation of white particulate dispersion WD2)

White fine particle dispersion WD2 was obtained similarly to the manufacture of white fine particle dispersion WD1 except that calcium carbonate (CWS-50; manufactured by Sakai Chemical Industry Co., Ltd .; particle diameter: 60 nm, refractive index: 1.57) was used as the white fine particles.

(Preparation of white particulate dispersion WD3)

White fine particle dispersion WD3 was obtained like the manufacture of white fine particle dispersion WD1 except that barium sulfate (BF-20; manufactured by Sakai Chemical Industry Co., Ltd .; particle diameter: 30 nm, refractive index: 1.64) was used as the white fine particles.

(Preparation of white particulate dispersion WD4)

White fine particle dispersion WD4 was obtained in the same manner as the manufacture of white fine particle dispersion WD1 except that aluminum oxide (“AEROXIDE” (registered trademark) Alu C; manufactured by Nippon Aerosil Co., Ltd. as the white fine particles was used: particle diameter: 13 nm, refractive index: 1.76) was used. .

(Preparation of white particulate dispersion WD5)

The white fine particle dispersion WD5 was obtained similarly to the manufacture of the white fine particle dispersion WD1 except that barium sulfate (BF-40; manufactured by Sakai Chemical Industry Co., Ltd .; particle diameter: 10 nm, refractive index: 1.64) was used as the white fine particles.

(Preparation of white particulate dispersion WD6)

White fine particle dispersion WD6 was obtained in the same manner as white fine particle dispersion WD1 except that barium sulfate (BF-1L; manufactured by Sakai Chemical Industry Co., Ltd .; particle diameter: 100 nm, refractive index: 1.64) was used as the white fine particles.

(Preparation of white particulate dispersion WD7)

The white fine particle dispersion WD7 was obtained similarly to the manufacture of the white fine particle dispersion WD1 except that barium sulfate (B-30; manufactured by Sakai Chemical Industry Co., Ltd .; particle diameter: 300 nm, refractive index: 1.64) was used as the white fine particles.

(Production of particulate dispersion WD8)

The fine particle dispersion WD8 was obtained like the manufacture of the white fine particle dispersion WD1 except that the acrylic resin fine particles (FS-106; manufactured by Nippon Paint Co., Ltd .; particle diameter: 100 nm, refractive index: 1.47) were used as the fine particles.

(Preparation of white particulate dispersion WD22)

4.24 kg of a 2.65% by mass aqueous solution of magnesium chloride and 4.14 kg of a 2.09% by weight aqueous solution of ammonium fluoride were mixed while stirring to obtain 8.38 kg of a slurry of colloidal particles of magnesium fluoride hydrate. Subsequently, it was concentrated using an ultrafiltration device to obtain 1.27 kg of a magnesium fluoride hydrate aqueous sol having a magnesium fluoride concentration of 5.9% by mass. With respect to 726 g of this sol, solvent substitution was performed while continuously charging 9 liters of isopropyl alcohol under reduced pressure with a rotary evaporator, and white particulate dispersion WD22 (concentration: 8.9 mass%, which is an isopropyl alcohol sol of magnesium fluoride hydrate) A particle size: 30 nm, and a refractive index: 1.38) were obtained.

(Preparation of white particulate dispersion WD23)

A white fine particle dispersion WD23 was obtained in the same manner as a white fine particle dispersion WD1 except that titanium oxide (TTO-55 (A); manufactured by Ishihara Sangyo Kaisha, Ltd .; particle diameter: 40 nm, refractive index: 2.71) was used as the white fine particles.

(Example 1)

After mixing the light-shielding material dispersion Bk1 (364 g) and the white particulate dispersion WD1 (364 g), polyamic acid A-1 (63 g), γ-butylolactone (82 g), N-methyl-2-pyrrolidone (87 g) , 3 methyl-3 methoxybutyl acetate (39 g) and surfactant LC951 (1 g; manufactured by Kusumoto Chemicals, Ltd.) were added, the total solid content concentration was 10 mass%, light-shielding material / white fine particles / resin (mass ratio) = 35 / A black resin composition LL1 of 35/30 was obtained. Further, the resin contains a non-volatile component of polyamic acid and surfactant in the dispersion.

50% by mass of a propylene glycol monomethyl ether acetate solution (18.7 g) of bisphenoxyethanol fluorine diacrylate as a multifunctional monomer in a light blocking material dispersion Bk4 (569.9 g) and dipentaerythritol hexaacrylate (DHPA; Nippon Kayaku Co., Ltd.) propylene glycol monomethyl ether acetate 50 mass% solution (25.9 g), as photopolymerization initiator IRGACURE (registered trademark) 369 (12.9 g), ADEKA (registered trademark), OPTOMER N-1919 (3.5 g; manufactured by Asahi Denka Kogyo KK), N, N'-tetraethyl-4,4'-diaminobenzophenone (1.3g) and a 10% by mass solution of propylene glycol monomethyl ether acetate (3.6g) of a silicone surfactant. A solution dissolved in 3-methyl-3-methoxy-butyl acetate (341.5 g) and propylene glycol monomethyl ether acetate (22.7 g) was added, and the total solid content concentration was 18 mass%, and the pigment / resin (mass ratio) = 70/30 A photosensitive resin composition UL1 was obtained. Further, the resin contains a nonvolatile component of an acrylic polymer (P-1), a polyfunctional monomer, a photopolymerization initiator, and a surfactant in the dispersion.

On a transparent alkali-free glass substrate (1737; manufactured by Corning Incorporated; 0.7 mm thick), a black resin composition LL1 was coated with a spin coater to a thickness of 0.7 µm after curing, and semi-cured at 120 ° C for 20 minutes. A semi-cured film of the light-shielding layer (A) having an OD value of 1.2 was obtained. Subsequently, the photosensitive black resin composition UL1 was applied with a spin coater so that the film thickness after curing was 0.7 µm, and prebaking was performed at 90 ° C for 10 minutes. For this coating film, MASK ALIGNER PEM-6M (manufactured by Union Optical Co., Ltd.) was used to expose ultraviolet light at an exposure dose of 200 mJ / cm 2 through a photomask.

Subsequently, a black matrix pattern that can be used for a color filter substrate was formed by developing with an alkali developer of a 0.5% by mass aqueous solution of tetramethylammonium hydroxide and subsequently washing with pure water. The resulting substrate was held in a hot air oven at 230 ° C. for 30 minutes to cure, thereby obtaining a black matrix substrate with an OD value of 4.0 with an OD value of 1.2, a light-blocking layer (A), and an OD value of 2.8, a light-blocking layer (B).

(Examples 2 to 7)

Black resin compositions LL2 to LL7 were obtained in the same manner as in Example 1 except that the white fine particle dispersions WD2 to WD7 were used instead of WD1 as the white fine particle dispersion to be used. A black matrix substrate having an OD value of 4.0 obtained by laminating the light-shielding layer (A) with an OD value of 1.2 and the light-shielding layer (B) having an OD value of 2.8 was obtained in the same manner as in Example 1 except that these black resin compositions LL2 to LL7 were used.

(Example 8)

After mixing the light-shielding material dispersion Bk2 (364 g) and the white particulate dispersion WD3 (364 g), polyamic acid A-1 (63 g), γ-butylolactone (82 g), N-methyl-2-pyrrolidone (87 g) , 3 methyl-3 methoxybutyl acetate (39 g) and surfactant LC951 (1 g) (manufactured by Kusumoto Chemicals, Ltd.), total solid content concentration of 10 mass%, light-shielding material / white fine particles / resin (mass ratio) = 35 A black resin composition LL8 of / 35/30 was obtained. A black matrix substrate having an OD value of 4.2 was obtained by laminating the light-blocking layer (A) with an OD value of 1.4 and the light-blocking layer (B) having an OD value of 2.8, similar to Example 1, except that this black resin composition LL8 was used.

(Example 9)

After mixing the light-shielding material dispersion Bk3 (364 g) and the white fine particle dispersion WD5 (364 g), polyamic acid A-1 (63 g), γ-butylolactone (82 g), N-methyl-2-pyrrolidone (87 g) , 3 methyl-3 methoxybutyl acetate (39 g) and surfactant LC951 (1 g) were added, the total solid content concentration was 10 mass%, light-shielding material / white fine particles / resin (mass ratio) = 35/35/30 black resin composition LL9 was obtained. A black matrix substrate having an OD value of 3.8 was obtained by laminating the light-blocking layer (A) with an OD value of 1.0 and the light-blocking layer (B) having an OD value of 2.8, similar to Example 1, except that this black resin composition LL9 was used.

(Example 10)

On a non-alkali glass (1737) substrate, which is a transparent substrate, the resin composition LL3 was coated with a spin coater so that the film thickness after curing was 0.7 µm, semi-cured at 120 ° C for 20 minutes, and the light-shielding layer having an OD value of 1.2 (A ) To obtain a semi-cured film. Subsequently, a positive photoresist (SRC-100; manufactured by Shipley Japan, Ltd.) was applied with a spin coater, and prebaking was performed at 90 ° C for 10 minutes. Using this MASK ALIGNER PEM-6M on this coating film, UV light is exposed through a positive photomask at an exposure amount of 200 mJ / cm 2, and a development of a positive resist and polyyi using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide After etching the mid precursor simultaneously, the positive resist was peeled off with methyl cellosolve acetate. Subsequently, it cured at 230 degreeC for 30 minutes, and produced the light-shielding layer (A) of OD value 1.2 with 0.7 micrometer thickness.

Light-shielding material dispersion Bk2 (728 g), polyamic acid A-1 (63 g), γ-butylolactone (82 g), N-methyl-2-pyrrolidone (87 g), 3 methyl-3 methoxybutyl acetate (39 g) ) And surfactant LC951 (1 g) were added to obtain a non-photosensitive black resin composition UL2 having a total solid content concentration of 10% by mass and a light-shielding material / resin (mass ratio) = 70/30.

Subsequently, the non-photosensitive resin composition UL2 was applied onto the substrate on which the light-shielding layer (A) was prepared, and then coated with a spin coater so that the film thickness after curing was 0.7 µm, and semi-cure was performed at 120 ° C for 20 minutes. Subsequently, a positive photoresist (SRC-100) was applied with a spin coater, and prebaking was performed at 90 ° C for 10 minutes. Using this MASK ALIGNER PEM-6M on this coating film, UV light is exposed through a positive photomask at an exposure amount of 200 mJ / cm 2, and a development of a positive resist and polyyi using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide After etching the mid precursor simultaneously, the positive resist was peeled off with methyl cellosolve acetate. Subsequently, it cured at 230 degreeC for 30 minutes, and obtained the resin black matrix board | substrate which laminated | stacked the light-shielding layer (A) of OD value 1.2 at 0.7 micrometers thickness and the light-shielding layer (B) of OD value 2.8 at 0.7 micrometers thickness.

(Example 11)

The black resin composition LL8 was obtained like Example 1 except having used the fine particle dispersion WD8 instead of WD1 as a used fine particle dispersion. A black matrix substrate having an OD value of 4.0 obtained by laminating a light-shielding layer (A) with an OD value of 1.2 and a light-shielding layer (B) having an OD value of 2.8 was obtained in the same manner as in Example 1 except that this black resin composition LL8 was used.

(Comparative Example 1)

Light-shielding material dispersion Bk1 (728 g), polyamic acid A-1 (63 g), γ-butylolactone (82 g), N-methyl-2-pyrrolidone (87 g), 3 methyl-3 methoxybutyl acetate (39 g) ) And surfactant LC951 (1 g) were added to obtain a black resin composition LL21 having a light-shielding material / resin (mass ratio) of 70/30 that does not contain white fine particles having a total solid content concentration of 10 mass% and a refractive index of 1.4 to 1.8.

On a non-alkali glass (1737) substrate which is a transparent substrate, the black resin composition LL21 was coated with a spin coater so that the film thickness after curing was 0.7 µm, and semi-cured at 120 ° C for 20 minutes to perform a light-shielding layer having an OD value of 2.5 ( The semi-cured film of A) was obtained. Subsequently, the photosensitive black resin composition UL1 was applied with a spin coater so that the film thickness after curing was 0.7 µm, and prebaking was performed at 90 ° C for 10 minutes. The coating film was exposed to ultraviolet light at an exposure amount of 200 mJ / cm 2 through a photomask using a MASK ALIGNER PEM-6M.

Subsequently, it developed with alkali developing solution of the 0.5 mass% aqueous solution of tetramethylammonium hydroxide, and it wash | cleaned with pure water, and the patterning substrate was obtained. The obtained patterning substrate was held in a hot air oven at 230 ° C. for 30 minutes to cure to obtain a black matrix substrate with an OD value of 5.3 stacked by a light blocking layer (A) having an OD value of 2.5 and a light blocking layer (B) having an OD value of 2.8.

(Comparative Example 2)

After mixing the light-shielding material dispersion Bk1 (364 g) and the white particulate dispersion WD22 (364 g), polyamic acid A-1 (63 g), γ-butylolactone (82 g), N-methyl-2-pyrrolidone (87 g) , 3 methyl-3 methoxybutyl acetate (39 g) and surfactant LC951 (1 g) were added to prepare a black resin composition LL22, but the particles were aggregated and the viscosity increased significantly, making it impossible to apply to the spin coater.

(Comparative Example 3)

The black resin composition LL23 was obtained like Example 1 except having used the white fine particle dispersion WD23. A resin black matrix substrate having an OD value of 4.0 obtained by laminating a light-shielding layer (A) with an OD value of 1.2 and a light-shielding layer (B) having an OD value of 2.8 was obtained in the same manner as in Example 1 except that this black resin composition LL23 was used.

<Evaluation Results>

Table 1 and Table 2 show the composition of the black resin composition prepared in Examples 1 to 11 and Comparative Examples 1 to 3 and the evaluation results of the produced BM substrate.

From the results of Tables 1 and 2, the BM substrates produced in Examples 1 to 11 are both preferably having a low reflectance chromaticity and reflectance to suppress the influence of external light, and also have high performance by sufficiently high OD and volume resistivity values. It was apparent that it was a black matrix substrate.

(Production of color filter substrate)

Green pigment (PG36; 44g), yellow pigment (PY138; 19g), polyamic acid A-2 (47g) and γ-butylolactone (890g) were added to the tank and stirred for 1 hour with a homomixer (manufactured by Primix Corporation). The G pigment preliminary dispersion G1 was obtained. Thereafter, 0.40 mmφ zirconium oxide beads (Toray Serum beads; manufactured by Toray Industries, Inc.) were supplied with a preliminary dispersion G1 to DYNO-MILL KDL (manufactured by Shinmaru Enterprises Corporation) 85% charged, and rotated at a speed of 11 m / s. Time dispersion was carried out to obtain a G pigment dispersion G1 having a solid content concentration of 7% by mass and a pigment / polymer (mass ratio) = 90/10. G pigment dispersion G1 was diluted with polyamic acid A-2 and a solvent to obtain a green resin composition.

A red pigment (PR254; 63 g) was added in place of the green pigment and sulfur pigment, and likewise, an R pigment dispersion R1 having a solid content concentration of 7% by mass and a pigment / polymer (mass ratio) = 90/10 was obtained. The R pigment dispersion R1 was diluted with polyamic acid A-2 and a solvent to obtain a red resin composition.

A blue pigment (PR15: 6; 63 g) was added instead of the green pigment and the yellow pigment, and similarly, a B pigment dispersion B1 having a solid content concentration of 7 mass% and a pigment / polymer (mass ratio) = 90/10 was obtained. The B pigment dispersion B1 was diluted with polyamic acid A-2 and a solvent to obtain a blue resin composition.

On each of the black matrix substrates prepared in Examples 1 to 11 and Comparative Examples 1 and 3, the red paste was dried and then applied to a thickness of 2.0 µm to pre-bak and form a polyimide precursor red colored film. A red pixel was formed by the same means as described above using a positive photoresist, and heat-cured by heating to 290 ° C. The green paste was applied in the same manner to form a green pixel, and heated to 290 ° C to perform thermal curing. Similarly, a blue paste was applied to form a blue pixel, and heated to 290 ° C to perform thermal curing.

(Production of liquid crystal display device)

After washing each of the obtained color filter substrates with a neutral detergent, an alignment film made of polyimide resin was applied by a printing method and heated at 250 ° C. for 10 minutes using a hot plate. The film thickness of the polyimide resin alignment film after heating was 0.07 µm. Thereafter, each color filter substrate was rubbed, and a sealant was applied by a dispensing method, and heated at 90 ° C for 10 minutes using a hot plate. On the other hand, the substrate on which the TFT array was formed on the glass substrate was similarly washed with a neutral detergent, and then an alignment film was applied and heated. Thereafter, a spherical spacer having a diameter of 5.5 µm was sprayed, and each color filter substrate coated with a sealing agent and a TFT substrate were stacked and heated in a oven at 160 ° C for 90 minutes while curing the sealing agent to obtain a cell. Each cell was left for 4 hours at a temperature of 120 ° C and a pressure of 13.3 Pa, and then left for 0.5 hour in nitrogen, and then the liquid crystal compound was charged again in a vacuum. The filling of the liquid crystal compound was performed by placing the cell in a chamber, lowering the pressure from room temperature to a pressure of 13.3 Pa, dipping the liquid crystal inlet into the liquid crystal and returning the pressure to normal pressure using nitrogen. After the liquid crystal was filled, the liquid crystal injection port was sealed with an ultraviolet curable resin. Subsequently, a polarizing plate was attached to the outside of the glass substrate of two cells to complete the cell. Further, the obtained cell was modularized to complete a liquid crystal display device.

As a result of observing the obtained liquid crystal display device, in the liquid crystal display devices provided with the black matrix substrates obtained in Examples 1 to 9 and Example 11, since the reflectance chromaticity and reflectance were both low, the display characteristics were good even when external light was shined. The liquid crystal display device provided with the black matrix substrate obtained in Example 10 was generally satisfactory, but was slightly dark because the black matrix pattern was misaligned. On the other hand, in the liquid crystal display device having the black matrix substrate obtained in Comparative Example 1 and Comparative Example 3, since the reflected chromaticity and reflectance are both high, when the external light was shined, it was observed that the black display was floating and the display quality was poor. .

(Industrial availability)

The black matrix substrate of the present invention can be used for a display device using a light source such as a cold cathode tube or LED, a color filter substrate for a liquid crystal display device, or a liquid crystal display device.

10: transparent substrate 11: resin BM (resin black matrix)
21: light-shielding layer (A) 22: light-shielding layer (B)
20: color filter substrate 23: pixels
24: Pixel 25: Pixel
26: overcoat film 28: transparent electrode
29: organic EL layer 30: back electrode layer
31: insulating film 32: substrate
33: extraction electrode 40: organic EL device

Claims (10)

In order, it has a transparent substrate, a light-blocking layer (A) and a light-blocking layer (B),
The optical concentration per thickness of the light-shielding layer (A) is lower than the optical concentration per thickness of the light-shielding layer (B), and the light-shielding layer (A) contains a light-shielding material and fine particles having a refractive index of 1.4 to 1.8. According to claim 1,
Black particles, characterized in that the fine particles having a refractive index of 1.4 to 1.8 are one or more fine particles selected from the group consisting of aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, and sodium metasilicate. Matrix substrate. The method of claim 1 or 2,
The black matrix substrate characterized in that the fine particles having a refractive index of 1.4 to 1.8 have a whiteness of 30% or more measured by a method in accordance with JIS P8148 (2001). The method of claim 1 or 2,
The transparent substrate is a black matrix substrate, which is made of polyimide resin. The light-shielding layer (A) and the light-shielding layer (B) of the black matrix substrate according to claim 1 or 2, have a pattern shape and are characterized by the presence of pixels colored in portions where no pattern is present. Color filter substrate. A light-emitting device comprising the color filter substrate according to claim 5 and a light-emitting element. The method of claim 6,
The light-emitting element is an organic EL element. A liquid crystal display device comprising, in order, the color filter substrate according to claim 5, a liquid crystal compound, and a counter substrate. A method for manufacturing a black matrix substrate according to claim 1 or 2,
A step of forming a layer of a composition containing a light-shielding material and fine particles having a refractive index of 1.4 to 1.8 above the transparent substrate,
A step of forming a layer of a photosensitive resin composition containing a light-shielding material thereon,
A method of manufacturing a black matrix substrate, comprising performing a pattern exposure to pattern processing the two layers using a developer or a solvent. A method of manufacturing a color filter comprising the step of forming a pixel in a portion where a pattern does not exist after the black matrix substrate is manufactured by the method for manufacturing a black matrix substrate according to claim 9.

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