TW201441676A - Black matrix substrate, manufacturing method thereof, color filter substrate, light emitting device, liquid crystal display device, and method of manufacturing color filter - Google Patents

Abstract

An object of the present invention is to provide a resin black matrix substrate on which a resin black matrix is formed, which has a sufficient optical density and a low reflectance. The present invention is a black matrix substrate comprising a transparent substrate, a light shielding layer (A) and a light shielding layer (B) in sequence, and the optical density per unit thickness of the light shielding layer (A) is lower than that of the light shielding layer (B) The optical density per unit thickness, the light shielding layer (A) contains 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 can be used for a color filter or a liquid crystal display device as its characteristics.

Description

Black matrix substrate

The present invention relates to a black matrix substrate which can be used for a color filter used in a liquid crystal display device or a light emitting device.

The liquid crystal display device has a structure in which a liquid crystal layer is interposed between two substrates, and exhibits brightness and darkness by an electro-optical response of the liquid crystal layer, and can be displayed in color by using a color filter substrate.

Conventionally, the mainstream of a black matrix which is formed on a color filter substrate to form a light-shielding layer is a metal thin film containing a chromium-based material. However, resin black containing a resin and a light-shielding material has been developed in order to reduce cost or reduce environmental pollution. matrix. A liquid crystal display device including a color filter substrate having a resin black matrix (the resin black matrix contains a light-shielding material such as carbon black) is excellent in visibility in the house, but when it is used outdoors, Deterioration of visibility caused by external light reflection from the black matrix becomes a problem.

In order to achieve a resin black matrix having a high optical density (hereinafter sometimes referred to as "OD (optical density) value) and low reflectance when viewed from the transparent substrate side, various studies have been made. For example, the following method is proposed: A method of using black colorant fine particles coated with an insulating material on the surface (Patent Document 1), a method of adding carbon black to titanium oxynitride (Patent Document 2), and a method using a mixture of titanium nitride and titanium carbide (patent Document 3), a method of forming a two-layer structure of a colored relief layer and a black relief layer (Patent Document 4), and a two-layer structure of a light absorption layer and a reflection light absorption layer containing shape anisotropic metal fine particles Method (Patent Document 5).

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-183511

Patent Document 2: Japanese Patent Laid-Open Publication No. 2006-209102

Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-95716

Patent Document 4: Japanese Patent Laid-Open No. Hei 8-146410

Patent Document 5: Japanese Patent Laid-Open Publication No. 2006-251237

However, since the high light-shielding material has a high reflectance in principle, it is extremely difficult for the resin black matrix to simultaneously achieve sufficient optical density and low reflectance. Further, the method of forming the resin black matrix into a two-layer structure has a problem that it is difficult to achieve a low reflectance over the entire visible light region, and high conductivity is caused by the use of metal fine particles, and display due to an electric field abnormality may occur. bad.

Accordingly, an object of the present invention is to provide a black matrix substrate formed with a resin black matrix having a sufficient optical density and a low reflectance, and further having a high resistance value and high reliability.

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

(1) A black matrix substrate comprising, in order, a transparent substrate, a light shielding layer (A), and a light shielding layer (B), and

The optical density per unit thickness of the light shielding layer (A) is lower than the optical density per unit 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 embodiment of the above invention.

(2) The black matrix substrate as described above, wherein the fine particles having a refractive index of 1.4 to 1.8 are selected from the group consisting of alumina, cerium oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, and metafluoric acid. More than one type of microparticles in a group consisting of sodium.

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

(4) The black matrix substrate according to any of the above, wherein the transparent substrate comprises a polyimide resin.

Further, the present invention provides the following using the black matrix substrate as described above.

(5) A color filter substrate, wherein the light shielding layer (A) and the light shielding layer (B) of the black matrix substrate according to any one of the above-mentioned items have a pattern shape, and a portion having no pattern exists Colored pixels.

(6) A light-emitting device comprising the color filter substrate and the light-emitting element as described above.

(7) The light-emitting device as described above, wherein the light-emitting element is an organic electroluminescence (EL) element.

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

Further, as described below, the present invention provides a preferred method for manufacturing the black matrix substrate and the color filter as described above.

(9) A method for producing a black matrix substrate, comprising the steps of: forming a layer containing a composition of a light-shielding material and a resin on a transparent substrate; and forming a layer of a photosensitive resin composition containing a light-shielding material thereon a step of patterning, patterning the above two layers by a developer or a solvent.

(10) A method of manufacturing a color filter comprising the step of disposing a pixel in a portion where no pattern is present after the black matrix substrate is manufactured by the method as described above.

According to the black matrix substrate of the present invention, the light shielding layer can achieve sufficient light blocking property for the purpose of not transmitting light of a backlight, so that it is possible to obtain not only a high contrast and sharp image but also Low reflectivity, so it is extremely excellent in visibility under external light and has high electrical reliability. Display device.

10‧‧‧Transparent substrate

11‧‧‧Resin BM (Resin Black Matrix)

20‧‧‧Color filter substrate

21‧‧‧Lighting layer (A)

22‧‧‧Lighting layer (B)

23, 24, 25‧ ‧ pixels

26‧‧‧Protective film

28‧‧‧Transparent electrode

29‧‧‧Organic EL layer

30‧‧‧Back electrode layer

31‧‧‧Insulation film

32‧‧‧Substrate

33‧‧‧Extraction electrode

34‧‧‧Sealant

40‧‧‧Organic EL components

L1, L2, L3‧‧‧ line width

1(a) to 1(e) are schematic cross-sectional views showing a plurality of embodiments of a black matrix substrate of the present invention.

Fig. 2 is a schematic cross-sectional view showing an embodiment of a black matrix substrate of the present invention.

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

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

In general, the optical density per unit thickness of the resin black matrix (hereinafter referred to as "resin BM") (the value obtained by dividing the optical density by the thickness, hereinafter referred to as "OD/T") is larger, and the reflectance is known. The higher. It is for the following reasons.

In general, in the case where the two opposite colorless transparent substances are in contact, the reflectance R of the light incident on the interface thereof can be expressed by the refractive index difference as shown in the following formula (1).

Reflectance R = (n _{1 -} n ₂ ) ² / (n ₁ + n ₂ ) ² (1)

(here, n ₁ and n ₂ respectively represent refractive indices of arbitrary colorless transparent substances n ₁ and n ₂ )

On the other hand, in the case of a substance such as a metal which is not colorless and transparent, the refractive index must be expressed by a complex refractive index. The complex refractive index N = n - iκ is used (n represents the real part of the refractive index of the substance n, and κ represents the extinction coefficient). In the case where the colorless transparent substance m is in contact with the non-colorless transparent substance n, the reflectance R of light incident perpendicularly from the substance m side to the interface thereof can be expressed by the following formula (2).

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

(here, m represents the refractive index of the colorless transparent substance m, n represents the real part of the refractive index of the substance n, and κ represents the extinction coefficient of the substance n)

According to the equation (2), the larger the extinction coefficient κ, the larger the reflectance. Further, when the extinction coefficient κ is 0, that is, when the substance n is colorless and transparent, the result is the same as the formula (1).

Moreover, the extinction coefficient is proportional to the absorption coefficient α at a certain wavelength. In addition, the absorption coefficient α can be approximated by a value obtained by multiplying OD/T by a constant. That is, the extinction coefficient κ is proportional to the value of OD/T, and when the formula (2) is used, it is understood that the larger the OD/T is, the higher the reflectance R of the interface between the substance m and the substance n is.

The inventors of the present invention have estimated that the substance m of the above formula (2) corresponds to a transparent substrate, and the substance n corresponds to the resin BM, and a low reflectance and a high light-shielding property which are required as characteristics of the resin BM are constant. Under a thick condition, it is in a trade-off relationship. It is effective to reduce OD/T for low reflection, but in this case, it is necessary to increase the film thickness of the black matrix in order to secure sufficient light shielding properties. A black matrix having a large film thickness causes alignment disorder of the liquid crystal to lower the contrast. Therefore, in order to solve this trade-off, it is considered that a layer having a small OD/T, a light-shielding layer (A) which can be called a low-optical density layer, and an OD/T are sequentially included on the transparent substrate. A black matrix substrate having a layer larger than the light shielding layer (A) and a light shielding layer (B) which can be called a high optical density layer is suitable for solving the problem. Further, the term "light shielding layer" as used herein is not limited to a layer that blocks light by 100%. According to the configuration of the black matrix substrate, since the light shielding layer (A) has a relatively low OD/T, reflection on the transparent substrate side at the interface on the transparent substrate side of the light shielding layer (A) is reduced. Since the light is also attenuated in the light shielding layer (A), the amount of reflection of light at the interface on the side of the light shielding layer (A) of the light shielding layer (B) is also reduced. As a result, the reflectance of the black matrix substrate of the present invention is lowered. Further, since the light shielding layer (B) is provided, the light transmitted through the light shielding layer (B) can have sufficient light blocking properties. In other words, it is estimated that the light from the side of the transparent substrate can simultaneously achieve low reflection and sufficient light blocking property by the configuration of such a black matrix substrate.

However, according to the study by the inventors of the present invention, it has been found that when the configuration is as described above, the light incident from the transparent substrate side is transmitted through the layer having a small OD/T and the OD of the layer having a large OD/T. Reflection occurs at the interface of the small layer side of T, and it is not simple to achieve low reflection of the resin BM required. Therefore, the inventors of the present invention have found that a black matrix substrate having such a configuration can simultaneously achieve sufficient light-shielding properties and low lightness by including a light-shielding material and fine particles having a refractive index of 1.4 to 1.8 in a layer having a small OD/T. Reflection, thereby completing the present invention.

The light shielding layer (A) of the present invention has a layer structure in which the optical density is not zero and is substantially opaque, and its OD/T is smaller than the OD/T of the light shielding layer (B). Further, the light shielding layer (B) of the present invention has a layer structure in which the optical density is not zero and is substantially opaque. Further, the so-called OD value in the present invention is used in a region having a wavelength of 380 nm to 700 nm.

OD value = log ₁₀ (I ₀ /I)

I ₀ : incident light intensity

I: transmitted light intensity

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

<<Light shielding layer (A)>>

<optical density>

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

The OD value of the entire light shielding layer present in the black matrix substrate of the present invention is preferably 3 or more, and more preferably 4 or more. Further, it is more preferably 6 or less, still more preferably 5 or less. When the overall OD value is too low, a part of the light having the backlight is transmitted to lower the contrast. On the other hand, if it is too high, the amount of the light shielding material added to the light shielding layer (B) and the light shielding layer (A) must be increased, and the reflectance tends to be high when the desired film thickness is formed. .

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

<microparticle>

The fine particles in the present invention are preferably fine particles which are substantially uncolored and are pale, transparent or white. Regarding the black pigment, or a pigment such as red, blue, green, purple, yellow, magenta or cyan, it is classified into a light-shielding material described later.

The components of the fine particles may be various kinds of ceramics, various resins, and the like in addition to white fine particles such as a pigment or a white pigment. However, as mentioned above, the refractive index must be 1.4 to 1.8.

Here, the refractive index of the fine particles means a refractive index under visible light, and a value corresponding to a refractive index at a wavelength of 589 nm of sodium D rays can be used as a representative value. The method of measuring the refractive index can be carried out by using a microparticle or a substance having the same composition as the microparticles as a sample, and measuring it by a liquid immersion method, that is, a Becke's line method. A method of calculating the refractive index by the Becker line method can prepare 30 samples of the same substance as the target fine particles, measure the refractive index of each, and calculate the refractive index from the average value thereof.

The fine particles used in the present invention must have a refractive index of from 1.4 to 1.8, preferably from 1.5 to 1.7. The low refractive index means that the density of the substance constituting the fine particles in principle is lowered. Therefore, such low-density particles have a problem that they are easily corroded by an organic solvent used as a dispersion medium in forming a light-shielding layer. Further complete processing of the black matrix substrate The agent properties become insufficient. On the other hand, when the refractive index is too high, the refractive index of the light shielding layer (A) becomes too large as compared with the transparent substrate, so that the reflection on the surface of the light shielding layer (A) on the transparent substrate side is increased, and as a result, there is a black matrix. The reflection of the substrate tends to be high. It is presumed that, according to the configuration of the present invention, by dispersing fine particles having a refractive index in the above range in a layer having a small OD/T, the influence of scattering of incident light by fine particles can be suppressed to a minimum, and OD/T can be made small. The refractive index of the layer becomes a value close to the transparent substrate, and the reflected light is attenuated in combination with the light shielding effect by the light shielding material.

Specific examples of the fine particles having a refractive index of 1.4 to 1.8 include fine particles of a resin such as an acrylic resin, a polyethylene resin, an anthrone fine particle, or a fluororesin. As a commercially available product, examples of the acrylic resin fine particles include FS-101, FS102, FS106, FS-107, FS-201, FS-301, FS-501, FS-701, and MG- manufactured by Nippon Paint. 155E, MG-451, MG-351, "TAFTIC" (registered trademark) F-120, F-167, etc. manufactured by Toyobo.

As described above, the fine particles which can be used in the present invention are preferably fine particles which are substantially uncolored and are pale, transparent or white, and are preferably white fine particles. Examples of the fine particles having a refractive index of 1.4 to 1.8 include minerals such as talc, mica or kaolin clay, oxides such as alumina or silica, barium sulfate or sulfuric acid. a sulfate such as calcium, a carbonate such as barium carbonate, calcium carbonate, magnesium carbonate or barium carbonate, sodium metasilicate or sodium stearate, but from the viewpoint of electrical reliability, it is preferably selected from alumina and barium oxide. The substance in the group consisting of barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, barium carbonate and sodium metasilicate, more preferably barium sulfate. Further, commercially available barium sulfate can be exemplified by "BARIFINE" (Note) Registered trademark) BF-10, BF-1, BF-20 or BF-40 (all of which are manufactured by 堺Chemical Industries, Ltd.). The fineness of the fine particles having a refractive index of 1.4 to 1.8 of the present invention measured by the method according to JIS P8148 (2001) is preferably 30% or more, and more preferably 50% or more. In the measurement of the whiteness of the fine particles, the fine particles are sufficiently pressurized so that the whiteness becomes a constant value, and the measurement is carried out by filling the measurement container with a pressure. Further, the above fine particles shown in this paragraph are fine particles having a whiteness of 30% or more.

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

The particle diameter of the fine particles is preferably 1 μm or less, preferably 5 nm to 500. Nm, and further preferably 10 nm to 100 nm. When the particle diameter 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 will increase and the reflectance will become high. Here, the particle diameter of the fine particles means the primary particle diameter of the fine particles. The primary particle diameter of the fine particles can be calculated by observing the primary particle diameters of 100 randomly selected microparticles by an electron microscope and obtaining the average value thereof. When the shape is other than the spherical shape, it can be calculated by calculating the average value of the maximum width and the minimum width obtained by observing a certain particle by an electron microscope as the primary particle diameter of the particle, and obtaining The average of 100 primary particle sizes. The fine particles having a particle diameter as described above preferably contain 90% by mass or more of the fine particles contained in the low optical density layer.

Examples of the method for producing the fine particles include minerals and the like which are raw materials. a pulverization method, a gas phase, a liquid phase, or a chemical method or substance under a solid layer Method. Examples of the pulverization method include a jet method, a hammer method, or a mill method. Examples of the chemical method in the gas phase include a chemical vapor deposition method (Chemical Vapor Deposition (CVD) method), an electric furnace method, a chemical flame method, or a plasma method. The chemical method in the liquid phase may, for example, be a precipitation method, an alkoxide method or a hydrothermal method. The chemical method in the solid phase is exemplified by a crystallization method. Examples of the physical method include a spray method, a solution combustion method, and a freeze drying method. Among them, since the particle diameter of the fine particles can be easily controlled, the precipitation method is preferred.

<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 more preferably contains a resin.

Examples of the light-shielding material include black organic pigments, mixed color organic pigments, and inorganic pigments. Examples of the black organic pigment include carbon black, resin-coated carbon black, perylene black, or aniline black. The mixed color organic pigment may, for example, be a pigment obtained by mixing a pigment such as red, blue, green, purple, yellow, magenta or cyan and being blackened. Examples of the inorganic pigment include graphite. Other examples include metal fine particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver. Further, examples thereof include oxides, composite oxides, sulfides, nitrides, and carbides of the metals described above. It is preferably one or more selected from the group consisting of titanium oxynitride reduced by nitrogen, that is, titanium black, titanium nitride, titanium carbide, and carbon black. Among them, more preferred is titanium oxynitride.

The term "titanium oxynitride" as used herein means a compound represented by TiN _x O _y (0 < x < 2.0, 0.1 < y < 2.0). However, if the content of oxygen is large, the degree of blackness is lowered, so x/y is preferably 0.1~10, more preferably 1~3.

The particle size of the light shielding material is preferably from 10 nm to 300 nm, more preferably 30 nm. ~100nm. The particle diameter of the light-shielding material herein means 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 in the case of the fine particles. When the particle size of the light-shielding material is too large, fine pattern processing tends to be difficult. On the other hand, when the particle diameter is too small, particles of the light-shielding material aggregate and the reflectance tends to be high.

The ratio of the light-shielding material in the light-shielding layer (A) is preferably 5% by mass. The above is further preferably 10% by mass or more. Further, the ratio thereof is 80% by mass or less, and more preferably 50% by mass or less. If the ratio of the light shielding material is small, it is difficult to obtain a sufficient optical density. On the other hand, when the ratio of the light shielding material is large, patterning of the light shielding layer (A) may become difficult.

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

The ratio of the resin which the light shielding layer (A) may contain is preferably 10% by mass or more. Further, it is preferably 30% by mass or more. Further, the ratio thereof is preferably 90% by mass or less, and more preferably 70% by mass or less.

The refractive index of the resin at a wavelength of 589 nm is preferably from 1.4 to 1.8, more preferably 1.5~1.7. For example, an epoxy resin, an acrylic resin, a siloxane oxide resin, or a polyimine resin can be mentioned. Among the above resins, since the heat resistance of the coating film is high, an acrylic resin or a polyimide resin is preferable, and a polyimide resin is more preferable. The polyimine resin referred to herein includes, in addition to a polyimine resin having a completely closed-loop structure, a closed loop of a polyamic acid and a poly-proline which is a precursor of a polyimide resin. Polyimine resin.

Polyimine resin can be heated and closed by using polyglycine as a precursor The cyclic oxime is imidized to form. Polylysine can be usually obtained by subjecting a compound having an acid anhydride group to a diamine compound by addition polymerization at 40 ° C to 100 ° C. It has a repeating structural unit represented by the following general formula (1). The polyimine resin in which a part of the polyamic acid is ring-closed has a proline structure represented by the following formula (2), and a part of the structure of the proline which is subjected to ring closure of the quinone imine (the following formula) 3) The quinone imine structure represented by the following general formula (4) in which the structure and the proline structure are all closed by a ruthenium ring.

[Chemical 2]

In the above formula (1) to formula (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 represents 1; Or an integer of 2.

In order to improve the heat resistance and insulation properties of the polyimide resin, The diamine compound of polyglycine is preferably an aromatic diamine compound, and the compound having an acid anhydride group is preferably an acid dianhydride.

Examples of the aromatic diamine compound include p-phenylenediamine and isophthalic acid. Amine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane , 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiyl Phenyl sulfide, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(trifluoromethyl)benzidine 9,9'-bis(4-aminophenyl)phosphonium 4,4'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 3,3'-diamino Diphenylamine, 2,4'-diaminodiphenylamine, 4,4'-diaminodibenzylamine, 2,2'-diaminodibenzylamine, 3,4'-diamino Dibenzylamine, 3,3'-diaminodibenzylamine, N,N'-bis-(4-amino-3-methylphenyl)ethylenediamine, 4,4'-diaminobenzoic acid Aniline, 3,4'-diaminobenzimidamide, 3,3'-diaminobenzimidil, 4,3'-diaminobenzamide, 2,4'-diamine Benzoquinone aniline, N,N'-p-phenylenebis-aminobenzamide, N,N'-p-phenylene-m-aminobenzamide, N,N'-m-phenylene Bis-aminobenzamide, N,N'-meta-phenyl bis-aminobenzamide, N,N'-dimethyl-N,N'-p-phenylene Aminobenzamide, N,N'-dimethyl-N,N'-p-phenylene-m-aminobenzamide, N,N'-diphenyl-N,N'-pair Phenylbis-p-aminobenzamide or N,N'-diphenyl-N,N'-p-phenylenem-aminobenzamide, preferably p-phenylenediamine, m-phenylenediamine , 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl hydrazine, 4,4'-Diaminodiphenylphosphonium, 9,9'-bis(4-aminophenyl)anthracene or 4,4'-diaminobenzimidamide.

Examples of the aromatic tetracarboxylic acid include 4,4'-oxydiphthalic dianhydride. 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 3,3',4,4 '-Diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-P-triphenyltetracarboxylic dianhydride or 3,3',4,4'- The cross-linked triphenyltetracarboxylic dianhydride or the like is preferably 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-benzophenonetetracarboxylic dianhydride or pyromellitic dianhydride. Further, when a fluorine-based tetracarboxylic dianhydride such as 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride is used, it is possible to obtain a polyethylene having good transparency in a short-wavelength region. Imine.

Compounds having an acid anhydride group and diamined to obtain polyamic acid In the addition polymerization of the compound, an acid anhydride such as maleic anhydride or phthalic anhydride may be added as a terminal blocking agent as needed. Further, in order to improve the adhesion to an inorganic substance such as a glass plate or a silicon wafer, an acid anhydride having a halogen atom or a diamine compound having a germanium atom may be used. The diamine having a halogen atom is preferably a peroxane diamine compound such as bis-3-(aminopropyl)tetramethylphosphonane. The ratio of the diamine having a halogen atom to the entire diamine compound is preferably from 1 mol% to 20 mol%. If the amount of the oxirane diamine compound is small, the effect of improving the adhesion cannot be obtained. On the other hand, if it is too much, the heat resistance of a film tends to fall. Further, in the case where the pattern of the light shielding layer is formed, development is carried out in an alkaline solution, and if the amount is too large, there is a problem that a residual film is generated during alkaline development due to excessive adhesion.

Compound having an acid anhydride group to obtain polyamic acid and diamine It is also possible to use an alicyclic acid dianhydride or an alicyclic diamine. Examples of the alicyclic acid dianhydride or the alicyclic diamine include 1,2,4,5-cyclohexanetetracarboxylic dianhydride and bicyclo [2.2.2] oct-7-ene-2,3. , 5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2-endo (endo)-3-endo-5-exo (exo)-6-exo-2,3,5,6- Tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2-exo-3-exo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.1 Heptane-2,3,5,6-tetracarboxylic dianhydride or decahydro-dimethyl bridge naphthalenetetracarboxylic 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 Alcohol bis(3-aminopropyl)ether, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro-5,5-undecane or 1,4- Butanediol bis(3-aminopropyl)ether.

The light shielding layer (A) may also contain an adhesion improver, a polymer dispersant or A surfactant or the like is used as another additive. The adhesion improving agent may, for example, be a silane coupling agent or a titanium coupling agent. The adhesion improving agent is preferably added in an amount of 0.2% by mass to 20% by mass based on the resin such as a polyimide resin or an acrylic resin. Examples of the polymer dispersant include a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, and a polyallylamine polymer dispersant. The polymer dispersant is usually added in an amount of 1% by mass to 40% by mass based on the light-shielding material. Examples of the surfactant include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether triethanolamine, a cationic surfactant such as stearyl acetate or lauryl trimethyl ammonium chloride, and a lauryl group. An amphoteric surfactant such as dimethylamine oxide or lauryl carboxymethylhydroxyethylimidazolium betaine, nonionic interface such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate The active agent is an anthrone-based surfactant or a fluorine-based surfactant having a main skeleton such as polydimethylsiloxane. The surfactant is usually added in an amount of 0.001% by mass to 10% by mass based on the pigment, and preferably 0.01% by mass to 1% by mass. When the amount of the surfactant is small, the coating property, the smoothness of the colored film, or the effect of preventing the benard cell may be insufficient. On the other hand, if there are too many surfactants, there is a coating film. Physical condition becomes bad. Each of the above additives contains a composition when the light shielding layer (A) is provided, but may be chemically reacted with the resin by heating or light irradiation to enter the chemical structure of the resin.

<<Light shielding layer (B)>>

<Composition of light shielding layer (B)>

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

The light-shielding material contained in the light-shielding layer (B) may be the same light-shielding material as the light-shielding layer (A). However, since the OD/T is large, it is preferably selected from the group consisting of carbon black, titanium oxynitride, titanium nitride, and titanium carbide. More than one, more preferably titanium nitride or titanium nitride. The term "titanium nitride" as used herein means a material containing titanium nitride as a main component and containing titanium oxide TiO ₂ , low-valent titanium oxide TinO _2n-1 (1≦n≦20) or titanium oxynitride as an auxiliary component. The titanium nitride particles contain an oxygen atom. However, in order to obtain a higher OD/T, the oxygen atom is preferably less, and the content of the oxygen atom is more preferably 12% by mass or less, still more preferably 8% by mass or less.

Examples of the synthesis of the titanium nitride particles include an electric furnace method or a thermoelectric plasma method. Gas phase reaction method. Among them, the thermal plasma method is preferred because the amount of impurities is small, the particle diameter is easily uniform, and the productivity is high. The method of generating the thermo-plasma may, for example, be a direct current arc discharge, a multi-layer arc discharge, a high frequency (radio frequency (RF)) plasma or a hybrid plasma (hybrid plasma). )Wait. Among them, high-frequency plasma is preferred because the impurities from the electrode are less mixed.

The particle size of the light shielding material is preferably from 10 nm to 300 nm, more preferably 30 nm. ~100nm. Here, the particle diameter of the light-shielding material means 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 in the case of the fine particles. When the particle diameter of the light-shielding material exceeds 300 nm, fine pattern processing may become difficult. On the other hand, when it is less than 10 nm, aggregation of particles tends to occur, and the reflectance tends to be high.

The ratio of the light shielding material in the light shielding layer (B) is preferably 10% by mass. The above is more preferably 40% by mass or more. Further, the ratio thereof is preferably 90% by mass or less, and more preferably 80% by mass. If the ratio of the light shielding material is small, it becomes difficult to obtain a sufficient optical density. On the other hand, if it is too much, it becomes difficult to pattern.

The ratio of the resin which the light shielding layer (B) may contain is preferably 10% by mass or more. Further, it is preferably 20% by mass or more. Further, the ratio thereof is preferably 90% by mass or less, and more preferably 60% by mass or less.

The resin which can be contained in the light shielding layer (B) can be exemplified by the light shielding layer (A). The resin is the same resin, and among them, an acrylic resin is preferable.

The acrylic resin is preferably an acrylic polymer having a carboxyl group, which is comparable Copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds are preferably used.

Examples of the unsaturated carboxylic acid which is a raw material of 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, and methacrylic acid. Propyl ester, acrylic acid Ester, n-butyl methacrylate, second butyl acrylate, second butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, third butyl methacrylate, acrylic acid An unsaturated carboxylic acid alkyl ester such as n-amyl ester, n-amyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate or benzyl methacrylate. Further, examples of the other ethylenically unsaturated compound include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene or α-methylstyrene. Further, examples thereof include an unsaturated carboxylic acid aminoalkyl ester such as aminoethyl acrylate or an unsaturated carboxylic acid glycidyl ester such as glycidyl acrylate or glycidyl methacrylate, vinyl acetate or vinyl propionate. Ethylene carboxylate and the like. Alternatively, grafting may be carried out by copolymerizing an oligomer having an unsaturated group at the terminal or a polymer as a macromonomer, for example, acrylonitrile or methacrylonitrile may be used. Or a vinyl cyanide compound such as α-chloroacrylonitrile, an aliphatic conjugated diene such as 1,3-butadiene or isoprene, or a polyphenyl group having an acryl fluorenyl group or a methacryl fluorenyl group at each terminal. Ethylene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate or polybutyl methacrylate. Among the copolymer components, a single one selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene is preferred. A copolymer of two components to four components of a monomer. The developing operation is usually performed while patterning the resin BM. In order to make the dissolution rate of the frequently used alkaline developing solution more appropriate, it is more preferably a weight average molecular weight Mw (using tetrahydrofuran as a carrier at a temperature of 23 ° C by gel permeation chromatography) Measure The value obtained by conversion using a calibration curve based on a standard polystyrene is 2,000 to 100,000 and the acid value is 70 to 150 (mgKOH/g).

In addition, the side chain may be previously included in the stage of the raw material of the light shielding layer (B). An acrylic resin having an ethylenically unsaturated group. By containing this material, the sensitivity at the time of exposure and development at the time of pattern processing of the resin BM can be improved. The ethylenically unsaturated group is preferably an acryloyl group or a methacryl group. The acrylic resin having an ethylenically unsaturated group in the side chain can be obtained by subjecting an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to an addition reaction of a carboxyl group of an acrylic resin having a carboxyl group.

An acrylic resin having an ethylenically unsaturated group in the side chain can be listed, for example CYCLOMER (registered trademark) P (Daicel Chemical Industries Co., Ltd.) or alkali-soluble cardo resin which is commercially available as an acrylic resin, but in order to make the ester solvent or alkaline The solubility of the developer is suitably adjusted, and the weight average molecular weight (Mw) is preferably from 2,000 to 100,000 and the acid value is from 70 to 150 (mgKOH/g).

The material of the light shielding layer (B) may further contain a polyfunctional acrylic monomer Or its reactants. The light-shielding layer is thereafter subjected to pattern processing, and usually the processing is performed in the order of pattern exposure and development. The above compound is polymerized and crosslinked by exposure to become insoluble in the developer. The polyfunctional acrylic monomer may, for example, be a polyfunctional acrylic monomer or oligomer. Examples of the polyfunctional acrylic monomer include bisphenol A diglycidyl ether (meth) acrylate, poly(meth) acrylate urethane, and modified bisphenol A epoxy (meth) acrylate. 1,6-hexanediol (methyl) adipic acid Ethyl ester, phthalic anhydride, propylene oxide (meth) acrylate, trimellitic acid diethylene glycol (meth) acrylate, rosin modified epoxy di(meth) acrylate, alkyd (meth) acrylate, oxime diacrylate oligomer, tripropylene glycol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, bisphenol A diglycidyl ether (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol Hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2,2-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]propane, bis[4- (3-propenyloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, bis[4-(3 -propenyloxy-2-hydroxypropoxy)phenyl]ether, 4,4'-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]cyclohexane, 9 ,9-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]indole, 9,9-bis[3-methyl-4-(3-propenyloxy-2- Propyloxy)phenyl]anthracene, 9,9-bis[3-chloro-4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, bisphenoxyethanol oxime diacrylate Ester, bisphenoxyethanol oxime dimethacrylate, biscresol oxime diacrylate and biscresol oxime dimethacrylate.

Suitably, the combination of the polyfunctional monomers or oligomers is preferred, preferably The compound having an energy group of 3 or more is more preferably a compound having 5 or more functional groups, and further preferably dipentaerythritol hexa(meth) acrylate or dipentaerythritol penta (meth) acrylate.

The light shielding layer contained in the light shielding layer (B) not only absorbs the visible light region Moreover, it also absorbs the tendency of ultraviolet rays effective for photocrosslinking, so it is preferable to even The amount of ultraviolet rays is also a combination of a highly sensitive polyfunctional acrylic monomer. Specifically, it is preferably a combination of dipentaerythritol hexa(meth) acrylate or dipentaerythritol penta (meth) acrylate. A (meth) acrylate having a large amount of an aromatic ring and having an anthracene ring having a high water repellency. The (meth) acrylate having an anthracene ring is preferably used in an amount of from 90 parts by mass to 40 parts by mass per 10 parts by mass to 60 parts by mass relative to dipentaerythritol hexa(meth) acrylate and dipentaerythritol penta (meth) acrylate. .

The photopolymerization initiator may be contained in the raw material of the light shielding layer (B). For example, Examples thereof include a benzophenone-based compound, an acetophenone-based compound, an oxanthone-based compound, an imidazole-based compound, a benzothiazole-based compound, a benzoxazole-based compound, an oxime ester compound, and an oxazole-based compound. An inorganic photopolymerization initiator such as a triazine compound, a phosphorus compound or a titanate.

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, Benzene dimethyl ketal, α-hydroxyisobutyl benzophenone, thioxanthone, 2-chlorothiazinone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinyl-1-propane, "Irgacure" (registered trademark) 369 (2-benzyl-2-dimethylamino-1-(4-morpholinylbenzene) ()-butanone), "Irgacure" (registered trademark) OXE01 (1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzylidene))), CGI -113 (2-[4-methylbenzyl]-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, tert-butylhydrazine) or CGI-242 (B Ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl)) (above, all steam Manufactured by Ciba Specialty Chemicals Co., Ltd., 1-chloroindole, 2,3-Dichloropurine, 3-chloro-2-methylindole, 2-ethylhydrazine, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1,2-benzopyrene, 1,4-Dimethyl hydrazine, 2-phenyl hydrazine, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoene Oxazole, 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-triazine or "Adeka" (registered trademark) "Optomer" (registered trademark) N-1818 or " Adeka" (registered trademark) "Optomer" (registered trademark) N-1919 and other carbazole compounds (all manufactured by Asahi Denki Kogyo Co., Ltd.). The raw material of the light shielding layer (B) may contain an adhesion improver, a polymer dispersant, a surfactant, or the like as another additive. Specifically, the same additives as those contained in the light shielding layer (A) are 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 more preferably 0.4 μm or more. Further, it is preferably 1.2 μm or less, and more preferably 1.0 μm or less. Further, the film thickness of the entire resin BM in which the two layers are combined is preferably 0.5 μm or more, and more preferably 1.0 μm or more. Further, the film thickness is preferably 2.0 μm or less, and more preferably 1.5 μm or less. If the overall film thickness is too small, an appropriate optical density may not be obtained. On the other hand, if it is too large, there is a case where the contrast due to the liquid crystal alignment failure is lowered.

The pattern shape of the resin BM formed on the black matrix substrate of the present invention may be, for example, a rectangle, a stripe, a square, a polygon, a wave, or a shape having irregularities. The width of the pattern is preferably from 3 μm to 30 μm, more preferably from 3 μm to 10 μm, still more preferably from 3 μm to 6 μm. When the pattern width is too large, the area of the opening of the pixel is small and the brightness is lowered. On the other hand, if the pattern width is too small, then There are cases where the pattern is lacking during processing.

The pattern of the light shielding layer (A) constituting the black matrix substrate of the present invention The pattern of the light shielding layer (B) is preferably substantially the same in order to maximize the opening area of the pixel and increase the brightness. Specifically, it means that the pattern shapes of the light shielding layer (A) such as a rectangular shape or a stripe shape and the light shielding layer (B) are substantially the same. The pattern width need not be strictly 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, still more preferably 0.5 μm or less.

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. When the resin BM having a large surface resistance value is formed, the insulating property of the color filter substrate is increased, and when a voltage is applied, the electric field is not disturbed, and good liquid crystal alignment property is obtained, and as a result, good quality can be obtained. A liquid crystal display device having a good display.

<<Transparent substrate>>

Examples of the transparent substrate include inorganic glass or organic plastic such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass coated with cerium oxide. The film or sheet of plastic has a refractive index of preferably 1.4 to 1.8, more preferably 1.5 to 1.7. The term "transparent" as used herein means that the transmittance is 80% or more, preferably 90% or more, over the entire wavelength range of 380 nm to 700 nm.

The film of the organic plastic is preferably a polyimide resin. By using a polyimide resin as a transparent substrate, a flexible black matrix substrate and a color filter substrate excellent in heat resistance and dimensional stability can be obtained.

The film of the polyimide resin can be obtained by using a polyamidene precursor such as polylysine The solution of the resin is applied onto a temporary substrate, and then dried and heated to prepare.

First, the polyimide composition precursor resin composition is applied to a temporary substrate on. Examples of the material of the temporary substrate include germanium wafers, ceramics, gallium arsenide, soda lime glass, or non-alkali glass. Examples of the method of applying the solution of the polyimine precursor resin onto the temporary substrate include a slit coating method, a spin coating method, and a spray coating method. The roll coating method or the bar coat method is preferably a spin coating method or a slit coating method. Next, the temporary substrate of the solution coated with the polyimide precursor resin was dried to obtain a polyimide composition precursor resin film. Examples of the drying method include a method using a hot plate, an oven, an infrared ray, or a vacuum chamber. In the case of using a hot plate, the temporary substrate is heated and dried on a jig or a fixture such as a pin (Proxy Pin) provided on the hot plate. Next, the polyimine precursor resin composition film is heated at 180 ° C to 400 ° C to be converted into a polyimide film.

The method for peeling the polyimide film from the temporary substrate can be listed, for example. A method of mechanically peeling, a method of immersing in a chemical liquid such as hydrofluoric acid or water, or a method of irradiating a laser to an interface between a polyimide film and a temporary substrate. Further, the black matrix substrate, the liquid crystal display device, or the light-emitting device may be directly produced without peeling the polyimide film from the temporary substrate, and then the polyimide film may be peeled off from the temporary substrate, but the dimensional stability is not considered. In terms of After the color filter substrate or the like is formed, peeling from the temporary substrate is performed.

<<Method of forming light shielding layer (A) and light shielding layer (B)>>

The method of forming the light shielding layer (A) and the light shielding layer (B) on the transparent substrate of the present invention can be exemplified by the following two methods.

1) A method of repeatedly performing a photolithography step

A light shielding layer (A) that has not been patterned is provided on the transparent substrate, and the layer is patterned. Thereafter, a light shielding layer (B) which has not been patterned is further provided, and the layer is patterned.

The method of patterning the light shielding layer (A) can be exemplified by photolithography. A method in which a light-shielding layer (A) is provided using a photosensitive resin composition, and a pattern is exposed and developed to obtain a pattern can be exemplified. Another method is to provide a light shielding layer (A) using a non-photosensitive resin composition. A photoresist is placed thereon, and the pattern is exposed to develop to form a pattern of the photoresist. At the same time as the development, the light shielding layer (A) may be patterned by etching the pattern of the photoresist as a mask with a developing solution. The pattern of the photoresist after development may be used as a mask, and the light shielding layer (A) may be patterned by etching with a solvent. The pattern of the light shielding layer (B) may be formed in the same manner as the patterning method of the light shielding layer (A) described above.

2) Method of performing a photolithography step

A light-shielding layer (A) which has not been patterned is provided on the transparent substrate, and a light-shielding layer (B) which has not been patterned is further provided, and the light-shielding layer (A) and the light-shielding layer (B) are patterned by photolithography. The photolithography method is to provide a photoresist on the light shielding layer (B) for pattern exposure, and to develop the photoresist while using the pattern of the photoresist as a mask for the light shielding layer (B) and the light shielding layer (A). Etching is performed to form a pattern. Or, After the pattern of the photoresist is formed, the light shielding layer (A) and the light shielding layer (B) are patterned by a solvent using a pattern of the photoresist as a mask. Further, as another method of performing photolithography, a light-shielding layer (A) which has not been patterned is provided on a transparent substrate, and an unpatterned light-shielding layer (B) containing a photosensitive resin composition is further provided. The light shielding layer (B) is patterned by photolithography, and the light shielding layer (A) is also patterned by a developing solution or a solvent. In this case, a photosensitive resin composition can also be used for the light shielding layer (A).

Figure for forming the light shielding layer (A) and the light shielding layer (B) in the black matrix substrate The details of the method of the case are explained. The light shielding layer (A) can be obtained by applying a resin composition as a raw material to a transparent substrate. Examples of the method of applying the resin composition on the transparent substrate include a spin coater, a bar coater, a blade coater, and a roll coater. Roll coater), die coater and screen print method. Other methods include a method of immersing a transparent substrate in a black resin composition and a method of spraying a black resin composition on a substrate. In order to improve coatability, the resin composition may further contain a solvent. For example, an ester, an aliphatic alcohol, a (poly) alkanediol ether solvent, a ketone, N-methyl-2- pyrrolidone, N, N- dimethyl acetamide, or N, N are mentioned. - a guanamine-based polar solvent or a lactone such as dimethylformamide. However, since the dispersion effect of the pigment as a light-shielding material is improved, a lactone or a mixed solvent containing a lactone as a main component is preferable. Here, the solvent containing a lactone as a main component means a solvent in which the lactone has the largest mass ratio among all the solvents. Further, the lactone is preferably an aliphatic cyclic ester compound having 3 to 12 carbon atoms. Examples of the lactones include β-propiolactone and γ- Butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone or ε-caprolactone. Among them, γ-butyrolactone is preferred from the viewpoint of solubility of the polyimide precursor. Further, examples of the solvent other than the lactones include 3-methyl-3-methoxybutanol, 3-methyl-3-methoxyacetic acid butyl ester, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Ester, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoterpene butoxide, isobutanol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate , methyl carbitol, methyl carbitol acetate, ethyl carbitol and ethyl carbitol acetate. The ratio of the solvent to the black resin composition used for the formation of the light-shielding layer (A) is preferably 70% by mass to 98% by mass, more preferably from the viewpoint of coatability and drying property. 80% by mass to 95% by mass.

Method for producing resin composition used in formation of light shielding layer (A) For example, a method in which a light-shielding material and fine particles are directly dispersed in a resin solution using a dispersing machine can be mentioned. Other methods include a method in which a light-shielding material and fine particles are dispersed in water or an organic solvent using a disperser to prepare a dispersion, and then the dispersion is mixed with a resin solution. Examples of the method of dispersing the light-shielding material and the fine particles include a ball mill, a sand grinder, a three roll mill, or a high-speed impact mill. Among them, a beads mill is preferred from the viewpoint of dispersion efficiency or microdispersion. Examples of the bead mill include a Co-ball mill, a basket mill, a pin mill, or a DYNO-MILL. The beads of the bead mill are, for example, preferably titania beads, zirconia beads or zircon beads. The diameter of the beads used in the dispersion is preferably from 0.01 mm to 5.0 mm, more preferably It is 0.03mm~1.0mm. When the primary particle diameter of the pigment or the particle diameter of the secondary particles formed by the aggregation of the primary particles is small, the beads used for the dispersion are preferably finely dispersed beads having a diameter of 0.03 mm to 0.10 mm. In this case, it is preferred to use a bead mill having a separator which is separated by a centrifugal separation method, which can separate the fine dispersed beads from the dispersion. On the other hand, in the case of dispersing a light-shielding material or fine particles containing coarse particles of a submicron degree, in order to obtain a sufficient pulverization force, a dispersed bead having a bead diameter of 0.10 mm or more is preferable. In addition, the light shielding material and the fine particles may be dispersed separately. In this case, in order to prevent agglomeration caused by solvent shock, it is preferred to use the same solvent.

By air drying, heat drying or vacuum drying, etc. by The coating film obtained by coating the resin composition on a transparent substrate is dried and hardened to form a dried film. In order to suppress uneven drying or uneven conveyance, it is preferred to dry-dry the transparent substrate coated with the black resin composition by a vacuum dryer equipped with a heating device, and then heat-semi-cure. .

Next, in order to form a light-shielding on the dried film of the above-mentioned light shielding layer (A) The layer (B) is coated with a black composition for which the OD/T is larger than the light shielding layer (B) of the light shielding layer (A) and dried.

The black composition for forming the light shielding layer (B) is preferably used to cover It is formed of a photosensitive black resin composition of a light material, a resin, a solvent, a polyfunctional acrylic monomer, and a photopolymerization initiator.

Photosensitive black resin composition used in formation of the light shielding layer (B) The solvent to be contained may suitably be selected from water or an organic solvent 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)alkyl glycol ether solvents, ketones, guanamine-based polar solvents, and lactone-based polar solvents. Examples of the esters include benzyl acetate (boiling point: 214 ° C), ethyl benzoate (boiling point: 213 ° C), methyl benzoate (boiling point: 200 ° C), diethyl malonate (boiling point: 199 ° C), acetic acid 2- Ethylhexyl ester (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 acetate (boiling point 181 ° C), cyclohexyl acetate (boiling point 174 ° C), acetic acid 3-methoxy-butyl ester (boiling point 173 ° C), ethyl acetate methyl acetate (boiling point 172 ° C) , 3-ethoxypropionic acid ethyl ester (boiling point 170 ° C), 2-ethylbutyl acetate (boiling point 162 ° C), isoamyl propionate (boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 °C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), amyl acetate (boiling point 150 ° C) or propylene glycol monomethyl ether acetate (boiling point 146 ° C) and the like.

Further, examples of the solvent other than the above include 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), diethyl ether (boiling point 135 ° C), methyl card Alcohol (boiling point 194 ° C), ethyl carbitol (boiling point 202 ° C), propylene glycol monomethyl ether (boiling point 120 ° C), propylene glycol monoethyl ether (boiling point 133 ° C), propylene glycol tert-butyl ether (boiling point 153 ° C) or dipropylene glycol (poly)alkyl glycol ether solvent such as monomethyl ether (boiling point 188 ° C); aliphatic ester such as ethyl acetate (boiling point 77 ° C), butyl acetate (boiling point 126 ° C) or isoamyl acetate (boiling point 142 ° C) Class; butanol (boiling point 118 ° C), 3- An aliphatic alcohol such as methyl-2-butanol (boiling point 112 ° C) or 3-methyl-3-methoxybutanol (boiling point 174 ° C); a ketone such as cyclopentanone or cyclohexanone; xylene ( Boiling point 144 ° C), ethylbenzene (boiling point 136 ° C) or solvent naphtha (petroleum fraction: boiling point 165 ° C ~ 178 ° C).

Furthermore, it is coated by a mold due to an increase in size of the transparent substrate. Since the application of the die coating apparatus is becoming mainstream, in order to achieve moderate volatility and drying property, a solvent mixture solvent having a boiling point of 150 to 200 ° C is preferably contained in an amount of 30% by mass to 75% by mass.

The method for producing the photosensitive resin composition which can be used for the formation of the light-shielding layer (B) is the same as the method of the light-shielding layer (A).

As described above, the resin composition for forming the light shielding layer (A) is applied and dried, and the photosensitive resin composition for forming the light shielding layer (B) is applied thereon and dried, and then passed through a mask. The ultraviolet light is irradiated from the exposure device, for example, development with an alkaline developer. As the alkaline developing solution, an aqueous solution of an aqueous solution of tetramethylammonium hydroxide or an alkali metal hydroxide can be used. For example, 0.01% by mass to 1% by mass of a surfactant such as a nonionic surfactant may be added to the developer.

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

Further, the pattern forming method of the above resin BM can also be applied to the case where the light shielding layer (A) does not contain fine particles having a refractive index of 1.4 to 1.8.

Next, a preferred shape of the resin BM will be described. Figure 1 is a representation A schematic view of several embodiments of a black matrix substrate of the present invention. The resin BM 11 including the light shielding layer (A) having a small OD/T and the light shielding layer (B) having a large OD/T is formed on the transparent substrate 10 in a pattern. The resin BM formed on the black matrix substrate of the present invention must have a layer sequentially as shown in FIG. 1(a) to FIG. 1(e), and may be any of the following patterns: a vertical pattern as shown in FIG. 1(a). The pattern of the mountain shape as shown in Fig. 1(b), the pattern of the inverted mountain pattern of Fig. 1(c), the pattern of the light shielding layer (B) of Fig. 1(d) is smaller than the pattern of the light shielding layer (A), The pattern of the light shielding layer (B) of FIG. 1(e) is arranged to be larger than the pattern of the light shielding layer (A). In order to narrow the line width of the resin BM and increase the aperture ratio of the pixel, it is preferable that the light shielding layer (A) 21 and the light shielding layer (B) 22 have the light shielding layer (A) 21 as shown in FIGS. 1( a ) to 1 ( c ). The width is approximately the same, and it is more preferable to laminate the mountain as shown in Fig. 1(b). Further, as shown in FIG. 2, the line width of the portion where the light shielding layer (A) 21 is in contact with the transparent substrate 10 is L1, and the line width of the boundary portion between the light shielding layer (A) 21 and the light shielding layer (B) 22 is set. When L2 is set and the line width of the top of the light shielding layer (B) 22 is 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, still more preferably 0.5 μm or less.

<<Using the black matrix substrate>>

The black matrix substrate of the present invention can be used for electronic materials, various displays, and the like. The utility model can effectively utilize the high optical density and low light reflection characteristics of the black matrix substrate of the invention for the partition wall of the plasma display panel (PDP), the dielectric pattern, the electrode (conductor circuit) pattern or the electron Part wiring pattern Production of light images. In order to improve the display characteristics of the color filter used in the color liquid crystal display device or the like, it is preferable to form the spacer and the peripheral portion of the colored pattern and the external light of the thin film transistor (TFT). A black matrix substrate provided with a resin BM is provided on the side.

<Color Filter>

In the color filter substrate disclosed in the present invention, a pixel colored by red, green, blue, or the like is formed in a portion where the pattern of the resin BM as the light shielding layer is not present by the black matrix substrate of the present invention.

The method for producing the color filter substrate of the present invention is exemplified by the following Method: After forming the resin BM on the transparent substrate, a pixel having a color selectivity of red (R), green (G) or blue (B) is formed. An over coat film may also be formed thereon as needed. Examples of the protective film include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a ruthenium-containing polyimide film, and a polyamidoxime. membrane. A transparent conductive film may be further formed on the protective film. Examples of the transparent conductive film include oxide films such as indium tin oxide (ITO). The method for producing the ITO film having a film thickness of about 0.1 μm may, for example, be a sputtering method or a vacuum deposition method. The material of the pixel is, for example, an inorganic film whose film thickness is controlled so as to transmit only arbitrary light, or a colored resin film which is dyed, dispersed with a dye or dispersed with a pigment.

The pigment dispersed in the pixels of the color filter substrate of the present invention is preferably It is a pigment excellent in light resistance, heat resistance and chemical resistance.

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

Examples of the yellow pigment include: pigment yellow (hereinafter It is called "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 It is called "PV") 19, PV23, PV29, PV30, PV32, PV36, PV37, PV38, PV40 and PV50.

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

These pigments can also be rosin-treated, acid-based or alkaline. Processing and other surface treatments. Further, a pigment derivative may be added as a dispersing agent.

The pixel of the color filter substrate of the present invention is a pigment dispersed In the case of a color resin film, examples of the binder resin to be used for the formation thereof include an acrylic resin, polyvinyl alcohol, polyamine, and polyimine, and from the viewpoints of heat resistance and chemical resistance, Good for polyimine.

The color filter substrate of the present invention can also form a fixed spacer (spacer). The fixed spacer refers to a spacer that is fixed to a specific position of the color filter substrate and that is in contact with the opposite substrate when the liquid crystal display device is fabricated. Thereby, a certain gap is maintained between the opposing substrate and the liquid crystal compound is filled between the gaps. The step of dispersing the spherical spacer or the step of kneading the rod shape spacer in the seal agent may be omitted in the manufacturing step of the liquid crystal display device by forming the fixed spacer.

<Liquid crystal display device, light-emitting device>

The liquid crystal display device of the present invention sequentially includes the color filter substrate, the liquid crystal compound, and the counter substrate.

Further, the light-emitting device of the present invention is characterized in that the color filter substrate of the present invention is bonded to a light-emitting element.

The light emitting element is preferably an organic EL element. The light-emitting device of the present invention can effectively utilize the high OD and low-reflection characteristics of the black matrix substrate, effectively shields unnecessary light from the light-emitting element under black display, and suppresses reflection of external light, thereby obtaining a display with high contrast and sharpness.

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

The light-emitting device shown in FIG. 3 is used to filter the color filter by using the sealant 34. The light-film substrate 20 is bonded to the organic EL element 40 as a light-emitting element.

The color filter substrate 20 includes: by the manufacturing method of the present invention The resulting black matrix substrate has red, green or blue pixels 23 to 25 formed in the opening portion thereof, and a protective layer 26. Here, the black matrix substrate provided in the color filter substrate 20 includes a substrate 10, a resin layer BM 11 in which a light shielding layer (A) 21 and a light shielding layer (B) 22 are laminated.

The organic EL element 40 includes a transparent electrode 28 and an organic electroluminescent layer. (hereinafter referred to as "organic EL layer") 29, back electrode layer 30, insulating film 31, substrate 32. An extraction electrode 33 that is in communication with an external power source. Here, the organic EL layer includes a hole transport layer, a light emitting layer, and an electron transport layer.

In FIG. 3, between the color filter substrate 20 and the organic EL element 40 A void, but a resin or a desiccant may be present as needed.

The material of the substrate 32 constituting the organic EL element 40 is, for example, glass. Transparent materials such as glass, film and plastic, and opaque materials such as aluminum, chrome or 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 a polyimide resin, an acrylic resin, an epoxy resin, and an anthrone resin, which can be formed by photolithography using a photosensitive material.

The back electrode layer 30 is located between the substrate 32 and the organic EL layer 29, A structure in which the organic EL layer emits light by applying a voltage between the back electrode layer 30 and the transparent electrode 28. The material of the back electrode layer may, for example, be magnesium, aluminum, indium, lithium, silver or aluminum oxide. The film thickness of the back electrode layer is usually 0.01 μm to 1 μm, for example, After forming a metal thin film by vapor deposition, sputtering, or the like, it is formed by patterning by photolithography.

The light of the organic EL layer 29 is preferably white light. According to the wavelength of white light It is preferable to change the color tone of the pixels 23 to 25 of the color filter substrate 20, thereby realizing a light-emitting device having a desired color reproduction range.

The material of the light-emitting layer is, for example, a cyclopentamine (cyclopentamine), tetraphenylbutadiene, triphenylamine, oxadiazole, pyrazoloquinoline, distyrylbenzene, distyryl extended aryl, silole, thiophene An organic compound having a skeleton such as pyridine, perinone, anthracene, oligothiophene or tridodecene diamine, and a pigment-based material such as an oxadiazole dimer or a pyrazoline dimer. Further, examples thereof include hydroxyquinoline aluminum complex, benzohydroxyquinolinium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, and hydrazine. Zinc porphyrin complex and ruthenium complex. A rare earth metal such as Al, Zn, Be, Tb, Eu or Dy is used as a central metal, and has a oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole or quinoline structure as a coordination. A metal complex compound such as a metal complex. Examples thereof include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polydecane derivatives, polyacetylene derivatives, polyfluorene derivatives, and polyvinylcarbazole derivatives. Molecular material. The film thickness of the light-emitting layer is usually 0.05 μm to 5 μm, and can be formed, for example, by a vapor deposition method, a spin coating method, a printing method, or an ink jet method.

In order to transmit the light of the organic EL layer 29, the transparent electrode 28 is transparent. The firing rate is preferably from 80% to 99%, more preferably from 90% to 99%. The material of the transparent electrode is for example There may be mentioned ITO, indium oxide, zinc oxide or tin dioxide. The thickness of the transparent electrode is usually 0.1 μm to 1 μm, and a thin film of a metal oxide can be formed by a vapor deposition method or a sputtering method, and then patterned by photolithography.

The material of the extraction electrode 33 is, for example, silver, aluminum, gold, chromium, nickel or molybdenum.

Further, a flexible light-emitting device can be obtained by bonding a flexible color filter substrate using a polyimide film as a substrate to a light-emitting element. Further, the flexible color filter substrate can be bonded to an organic EL element as a light-emitting element to produce a flexible organic EL display.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples and comparative examples.

<Evaluation method>

[Refractive index of microparticles]

The refractive index was determined by the Beck line method. A sample of 30 substances which are the same as the target fine particles was prepared, and the refractive indices were measured one by one, and the refractive index was calculated from the average value thereof.

[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 of incident light and transmitted light is measured using a microscopic spectroscope (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.), and is calculated according to the following formula (7). The region having a wavelength of 380 nm to 700 nm is calculated in units of 5 nm, and is obtained by using the average value of the obtained values.

OD value = log ₁₀ (I ₀ /I)... Equation (7)

I ₀ : incident light intensity

I: transmitted light intensity.

[reflective chromaticity]

A resin BM having a predetermined film thickness was formed on an alkali-free glass having a thickness of 0.7 mm, and an absolute reflection measurement at an incident angle of 5° from the glass surface was carried out using an ultraviolet-visible spectrophotometer (UV-2450; manufactured by Shimadzu Corporation). . Calculate the chromaticity values (a ^* , b ^* ) of the D65 light source calculated by the International Commission on Illumination (CIE) L ^* a ^* b ^* color system based on the obtained spectrum. The Y (reflectance) under the D65 light source calculated by the CIE XYZ color system is used, and the reflection chromaticity is determined based on the following criterion.

A: The reflectance is 4.2 or more and less than 4.7, and a ^* and b ^* are 1.0 or less.

B: the reflectance is 4.2 or more and less than 4.7, and a ^* and b ^* exceed 1.0 and are 2.0 or less.

C: the reflectance is 4.2 or more and less than 4.7, and a ^* or b ^* exceeds 2.0.

D: the reflectance is 4.7 or more and less than 5.2, and a ^* and b ^* are 1.0 or less.

E: the reflectance is 4.7 or more and less than 5.2, and a ^* and b ^* exceed 1.0 and are 2.0 or less.

F: the reflectance is 4.7 or more and less than 5.2, and a ^* or b ^* exceeds 2.0.

G: The reflectance is 5.2 or more.

[surface resistance value]

The surface resistance value (Ω/□) was measured at a voltage of 10 V using a Hiresta UP MCP-HT450 (manufactured by Mitsubishi Chemical Analytic), and the insulation property was determined based on the following criteria.

Excellent: extremely high insulation for measuring limits above (10 ¹⁵ Ω/□)

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

Bad: Less than 10 ⁸ Ω/□ and insufficient insulation.

[particle size]

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

<Manufacturing example>

(Synthesis of polyaminic acid A-1)

Add 4,4'-diaminophenyl ether (0.30 molar equivalent), p-phenylenediamine (0.65 molar equivalent), bis(3-aminopropyl)tetramethyldioxane (0.05 mole) Equivalent), 850 g of γ-butyrolactone and 850 g of N-methyl-2-pyrrolidone, adding 3,3',4,4'-oxydiphthalic dianhydride (0.9975 mol equivalent) at 80 The reaction was carried out at ° C for 3 hours. Further, maleic anhydride (0.02 mol equivalent) was added, and the mixture was reacted at 80 ° C for 1 hour to obtain a solution of polyproline A-1 (polymer concentration: 20% by mass).

(Synthesis of polyaminic acid A-2)

Add 4,4'-diaminophenyl ether (0.95 mole equivalent), bis(3-aminopropyl)tetramethyldioxane (0.05 molar equivalent) and γ-butyrolactone 1700 g (100) %), adding pyromellitic dianhydride (0.49 molar equivalent) and benzophenone tetracarboxylic dianhydride (0.50) Mohr equivalent), 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 solution of polyglycine A-2 (polymer concentration: 20% by mass).

(Synthesis of acrylic polymer (P-1))

To a 1000 cc four-neck flask (flask with four necks), 100 g of isopropyl alcohol was added thereto, and the mixture was kept at 80 ° C in an oil bath, and subjected to a nitrogen seal and stirring. A dropping funnel was added dropwise a mixture of 30 g of methyl methacrylate, 40 g of styrene, 30 g of methacrylic acid and 2 g of N,N-azobisisobutyronitrile over 30 minutes. After the reaction was continued for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the mixture was returned to normal temperature to complete the polymerization. As a result, a solution containing a methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio: 30/40/30) was obtained. After adding 100 g of isopropyl alcohol to the solution, 40 g of glycidyl methacrylate and 3 g of triethylbenzylammonium chloride were added and allowed to react for 3 hours while maintaining the temperature at 75 ° C, and the mixture was purified with purified water. Reprecipitation, filtration, and drying, thereby obtaining a weight average molecular weight (Mw, which was measured by gel permeation chromatography at a temperature of 23 ° C using tetrahydrofuran as a carrier, and a molecular weight converted using a calibration curve using standard polystyrene) 40,000, acrylic acid (P-1) powder having an acid value of 110 (mgKOH/g). Here, the reaction rate of glycidyl methacrylate was determined from the change in the acid value of the polymer before and after the reaction, and as a result, it was 70%, and the amount of addition was 0.73 equivalent.

(Production of light-shielding material dispersion Bk1)

The thermoelectric plasma method is to apply 4.0 kg of titanium dioxide powder having an average primary particle diameter of 40 nm. After being charged into the reaction furnace, ammonia gas was introduced at a linear velocity of 3 cm/sec in the furnace, and a reaction was carried out at a furnace temperature of 750 ° C for 6 hours to obtain titanium oxynitride (particle diameter: 40 nm, titanium content: 70.6 mass%, nitrogen content: 18.8% by mass, oxygen content: 8.64 mass%) 3.2 kg. The titanium oxynitride (96 g), polylysine solution A-1 (120 g), γ-butyrolactone (114 g), N-methyl-2-pyrrolidone (538 g), and 3-methyl-3 - butyl methoxyacetate (132 g) was added to a tank, and stirred for 1 hour using a homomixer (manufactured by a special machine), and then used with a 70% filled zirconia beads of 0.05 mmφ (YTZ ball) The Ultra Apex Mill (manufactured by Sika Industrial Co., Ltd.) of the centrifugal separation separator manufactured by NIKKATO was dispersed at a number of revolutions of 8 m/s for 2 hours to obtain a solid content concentration of 12% by mass and a pigment/resin (mass ratio) = 80. /20 of the light-shielding material dispersion Bk1.

(Production of light-shielding material dispersion Bk2)

Titanium nitride particles (manufactured by Wako Pure Chemical Industries, Ltd.; particle diameter: 50 nm, titanium content: 74.3 mass%, nitrogen content: 20.3% by mass, oxygen content: 2.94% by mass) were used as pigments, and The light-shielding material dispersion Bk1 was obtained in the same manner as in the production of the light-shielding material dispersion Bk1.

(Production of light-shielding material dispersion Bk3)

The light-shielding material dispersion liquid Bk3 was obtained in the same manner as the production of the light-shielding material dispersion liquid Bk1, except that carbon black (MA100; manufactured by Mitsubishi Chemical Corporation; particle size: 24 nm) was used as the pigment.

(Production of light-shielding material dispersion Bk4)

Titanium nitride particles (manufactured by Wako Pure Chemical Industries Co., Ltd.; particle size: 50 Nm, titanium content: 74.3 mass%, nitrogen content: 20.3% by mass, oxygen content: 2.94% by mass) (200 g), acrylic polymer (P-1) 3-methyl-3-methoxybutanol 45 The mass % solution (100 g) and propylene glycol tert-butyl ether (700 g) were added to the storage tank, and after stirring for 1 hour with a homomixer, Ultra Apex Mill equipped with a centrifugal separator having 70% of zirconia beads filled with 0.05 mmφ was used. The dispersion was carried out for 2 hours at a number of revolutions of 8 m/s to obtain a light-shielding material dispersion liquid Bk4 having a solid content concentration of 24.5% by mass and a pigment/resin (mass ratio) of 82/18.

(production of white fine particle dispersion WD1)

Cerium oxide as white fine particles ("AEROSIL" (registered trademark) OX50; manufactured by Nippon Aerosil Co., Ltd.; particle size: 40 nm, refractive index: 1.45) (96 g), poly-proline solution A- 1 (120 g), γ-butyrolactone (114 g), N-methyl-2-pyrrolidone (538 g) and 3-methyl-3-methoxyacetic acid butyl ester (132 g) were added to the storage tank, After stirring for 1 hour with a homomixer, an Ultra Apex Mill equipped with a centrifugal separator of 70% zirconia beads of 70% was dispersed at a number of revolutions of 8 m/s for 2 hours to obtain a solid content concentration of 12% by mass, pigment/resin. (mass ratio) = 80/20 white fine particle dispersion WD1.

(production of white fine particle dispersion WD2)

White fine particle dispersion was obtained in the same manner as in the production of the white fine particle dispersion WD1, except that calcium carbonate (CWS-50; manufactured by Seiko Chemical Co., Ltd.; particle diameter: 60 nm, refractive index: 1.57) was used as the white fine particles. Liquid WD2.

(Production of white particle dispersion WD3)

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

(production of white particle dispersion WD4)

Alumina ("AEROXIDE" (registered trademark) Alu C; manufactured by Japan Aerotech Co., Ltd.; particle size: 13 nm, refractive index: 1.76) was used as the white fine particles, and was produced in the same manner as the white fine particle dispersion WD1. The way to obtain the white particle dispersion WD4.

(production of white particle dispersion WD5)

White fine particle dispersion was obtained in the same manner as in the production of the white fine particle dispersion WD1, except that barium sulfate (BF-40; manufactured by Seiko Chemical Industry Co., Ltd.; particle diameter: 10 nm, refractive index: 1.64) was used as the white fine particles. Liquid WD5.

(Production of white fine particle dispersion WD6)

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

(Production of white particle dispersion WD7)

White fine particle dispersion was obtained in the same manner as in the production of the white fine particle dispersion WD1, except that barium sulfate (B-30; manufactured by Seiko Chemical Industry Co., Ltd.; particle diameter: 300 nm, refractive index: 1.64) was used as the white fine particles. Liquid WD7.

(Production of Microparticle Dispersion WD8)

Acrylic resin microparticles (FS-106; Japan Paint Co., Ltd. The fine particle dispersion WD8 was obtained in the same manner as in the production of the white fine particle dispersion WD1, except that the particle diameter was 100 nm, and the refractive index was 1.47.

(production of white particle dispersion WD22)

4.24 kg of a 2.65 mass% aqueous solution of magnesium chloride and 4.14 kg of an ammonium fluoride aqueous solution of 2.09 wt% were mixed while stirring to obtain 8.38 kg of a slurry of colloid particles of magnesium fluoride hydrate. Subsequently, the mixture was concentrated using an ultrafiltration apparatus to obtain 1.27 kg of a magnesium fluoride hydrate aqueous sol (sol) having a magnesium fluoride concentration of 5.9% by mass. Further, 726 g of the sol was further subjected to solvent replacement while continuously charging 9 liters of isopropyl alcohol under reduced pressure by a rotary evaporator to obtain isopropanol as magnesium fluoride hydrate. White fine particle dispersion WD22 of sol (concentration: 8.9% by mass, particle diameter: 30 nm, refractive index: 1.38).

(production of white fine particle dispersion WD23)

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

(Example 1)

After mixing the light-shielding material dispersion Bk1 (364 g) with the white fine particle dispersion WD1 (364 g), poly-proline acid A-1 (63 g), γ-butyrolactone (82 g), and N-methyl-2-pyrrole were added. Acetone (87g), 3-methyl-3-methoxyacetic acid butyl ester (39g) and surfactant LC951 (1g; manufactured by Nanben Chemical Co., Ltd.) to obtain a total solid concentration of 10 masses %, light-shielding material / white fine particle / resin (mass ratio) = 35/35/30 black resin composition LL1. Further, the resin contains a polyacetin in the dispersion and a nonvolatile component of the surfactant.

Addition to the light-shielding material dispersion Bk4 (569.9g) will be used as a polyfunctional Monopropylene propylene glycol monomethyl ether acetate 50% by mass solution (18.7g) and dipentaerythritol hexaacrylate (DHPA; manufactured by Nippon Kayaku Co., Ltd.) propylene glycol monomethyl ether Acetate 50% by mass solution (25.9 g), Irgacure (registered trademark) 369 (12.9 g) as a photopolymerization initiator, Adeka (registered trademark) Optomer N-1919 (3.5 g; manufactured by Asahi Kasei Kogyo Co., Ltd. , N,N'-tetraethyl-4,4'-diaminobenzophenone (1.3g) and an oxime ketone surfactant propylene glycol monomethyl ether acetate 10% by mass solution (3.6g) A solution obtained by dissolving 3-methoxy-butylacetic acid 3-methyl ester (341.5 g) and propylene glycol monomethyl ether acetate (22.7 g) to obtain a total solid content concentration of 18% by mass, pigment/resin (mass ratio) = 70/30 photosensitive resin composition UL1. Further, the resin contains a nonvolatile component of the acrylic polymer (P-1), the polyfunctional monomer, the photopolymerization initiator, and the surfactant in the dispersion.

The black resin composition LL1 was applied to an alkali-free glass (1737; manufactured by Corning; thickness: 0.7 mm) as a transparent substrate by a spin coater so that the film thickness after curing was 0.7 μm. The film was semi-hardened at 120 ° C for 20 minutes to obtain a semi-cured film of the light-shielding layer (A) having an OD value of 1.2. Next, the photosensitive black resin composition UL1 was applied by a spin coater so that the film thickness after hardening became 0.7 μm, and prebake was performed at 90 ° C for 10 minutes. The coating film, using a mask aligner machine (mask aligner) PEM-6M (optical joint (Union Optical) Co., Ltd.), through a mask (photomasks) to an exposure amount 200mJ / cm ² of UV exposure .

Secondly, the basicity of a 0.5% by mass aqueous solution of tetramethylammonium hydroxide The developer is developed, and then washed with pure water, thereby forming a black matrix pattern usable for the color filter substrate. The obtained substrate was cured in a hot air oven at 230 ° C for 30 minutes, thereby obtaining a black layer having an OD value of 4.0 of a light shielding layer (A) having an OD value of 1.2 and a light shielding layer (B) having an OD value of 2.8. Matrix substrate.

(Example 2 to Example 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 liquid. The OD value of the light shielding layer (A) having 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 the black resin compositions LL2 to LL7 were used. Black matrix substrate.

(Example 8)

After mixing the light-shielding material dispersion Bk2 (364 g) with the white fine particle dispersion WD3 (364 g), poly-proline acid A-1 (63 g), γ-butyrolactone (82 g), and N-methyl-2-pyrrole were added. A ketone (87 g), 3-methyl-3-methoxyacetic acid butyl ester (39 g), and a surfactant LC951 (1 g) (manufactured by Nanben Chemical Co., Ltd.) to obtain a total solid content concentration of 10% by mass, a light-shielding material/white fine particles / Resin (mass ratio) = 35/35/30 black resin composition LL8. The black resin composition LL8 was used, and the same as Example 1 In the same manner, a black matrix substrate having an OD value of 4.2 with a light shielding layer (A) having an OD value of 1.4 and a light shielding layer (B) having an OD value of 2.8 was obtained.

(Example 9)

After mixing the light-shielding material dispersion Bk3 (364 g) with the white fine particle dispersion WD5 (364 g), poly-proline acid A-1 (63 g), γ-butyrolactone (82 g), and N-methyl-2-pyrrole were added. Iridone (87g), 3-methyl-3-methoxyacetic acid butyl ester (39g) and surfactant LC951 (1g), to obtain a total solid content concentration of 10% by mass, shading material / white fine particles / resin (mass ratio ) = 35/35/30 black resin composition LL9. A black matrix substrate having an OD value of 3.8 with a light shielding layer (A) having an OD value of 1.0 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 the black resin composition LL9 was used. .

(Embodiment 10)

The resin composition LL3 was applied onto an alkali-free glass (1737) substrate as a transparent substrate so that the film thickness after curing was 0.7 μm by a spin coater, and semi-hardened at 120 ° C for 20 minutes to obtain an OD value. A semi-hardened film of the light-shielding layer (A) of 1.2. Next, a positive photoresist (SRC-100; manufactured by Shipley Co., Ltd.) was applied by a spin coater, and prebaked at 90 ° C for 10 minutes. The coating film, using a mask aligner machine PEM-6M, exposed to ultraviolet rays through a positive-type photomask with an exposure amount of 200mJ / cm ² using a tetramethylammonium hydroxide aqueous solution of 2.38% by mass simultaneously After the development of the positive resist and the etching of the polyimide precursor, the positive resist was peeled off by the methyl cellosolve acetate. Then, it was hardened at 230 ° C for 30 minutes to prepare a light shielding layer (A) having a thickness of 0.7 μm and an OD value of 1.2.

Adding polyaminic acid A-1 (63) to the light-shielding material dispersion Bk2 (728g) g), γ-butyrolactone (82g), N-methyl-2-pyrrolidone (87g), 3-methyl-3-methoxyacetic acid butyl ester (39g) and surfactant LC951 (1g) 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 was obtained.

Then, the non-photosensitive resin composition UL2 was applied onto the substrate on which the light-shielding layer (A) was formed by a spin coater so that the film thickness after curing was 0.7 μm, and semi-cured at 120 ° C for 20 minutes. Then, a positive photoresist (SRC-100) was applied by a spin coater, and prebaked at 90 ° C for 10 minutes. For the coating film, a mask alignment exposure machine PEM-6M was used, and ultraviolet light exposure was performed at a exposure amount of 200 mJ/cm ² through a photomask for positive type, and simultaneous use of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was carried out simultaneously. After the development of the positive resist and the etching of the polyimide precursor, the positive resist was peeled off by the methyl cellosolve acetate. Then, it was hardened at 230 ° C for 30 minutes to obtain a resin black matrix substrate in which a light shielding layer (A) having a thickness of 0.7 μm and an OD value of 1.2 and a light shielding layer (B) having a thickness of 0.7 μm and an OD value of 2.8 were laminated.

(Example 11)

A black resin composition LL8 was obtained in the same manner as in Example 1 except that the fine particle dispersion WD8 was used instead of WD1 as the fine particle dispersion liquid to be used. A black matrix substrate having an OD value of 4.0 of a light shielding layer (A) having 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 the black resin composition LL8 was used. .

(Comparative Example 1)

Polyphthalic acid A-1 (63 g), γ-butyrolactone (82 g), N-methyl-2-pyrrolidone (87 g), 3-methyl- were added to the light-shielding material dispersion Bk1 (728 g). Butyl 3-methoxyacetate (39 g) and surfactant LC951 (1 g), a light-shielding material/resin (mass ratio) of white fine particles having a total solid content concentration of 10% by mass and having a refractive index of 1.4 to 1.8 = 70/30 black resin composition LL21.

The black resin composition LL21 was applied onto an alkali-free glass (1737) substrate as a transparent substrate so that the film thickness after curing was 0.7 μm by a spin coater, and semi-hardened at 120 ° C for 20 minutes to obtain an OD. A semi-hardened film of the light shielding layer (A) having a value of 2.5. Next, the photosensitive black resin composition UL1 was applied by a spin coater so that the film thickness after hardening became 0.7 μm, and prebaked at 90 ° C for 10 minutes. The coating film was subjected to ultraviolet exposure using a mask alignment exposure machine PEM-6M through a photomask at an exposure amount of 200 mJ/cm ² .

Secondly, the basicity of a 0.5% by mass aqueous solution of tetramethylammonium hydroxide The developer is developed, and then washed with pure water, thereby obtaining a patterned substrate. The obtained patterned substrate was cured in a hot air oven at 230 ° C for 30 minutes, thereby obtaining an OD value of 5.3 of a light shielding layer (A) having an OD value of 2.5 and a light shielding layer (B) having an OD value of 2.8. Black matrix substrate.

(Comparative Example 2)

After mixing the light-shielding material dispersion Bk1 (364 g) with the white fine particle dispersion WD22 (364 g), poly-proline acid A-1 (63 g), γ-butyrolactone (82 g), and N-methyl-2-pyrrole were added. Pyridone (87g), 3-methyl-3-methoxyacetic acid butyl ester (39g) and The surfactant resin LC951 (1 g) was used to produce the black resin composition LL22. However, the particles were agglomerated and the viscosity was remarkably increased, and the coating could not be performed by a spin coater.

(Comparative Example 3)

A black resin composition LL23 was obtained in the same manner as in Example 1 except that the white fine particle dispersion WD23 was used. A resin black matrix having an OD value of 4.0 of a light shielding layer (A) having 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 the black resin composition LL23 was used. Substrate.

<evaluation result>

The composition of the black resin composition produced in Examples 1 to 11 and Comparative Examples 1 to 3 and the evaluation results of the produced BM substrate are shown in Tables 1 and 2.

It can be clarified from the results of Tables 1 and 2 that in Examples 1 to 11 Since the produced BM substrate has a low reflection chromaticity and a low reflectance, it is preferable to suppress the influence of external light, and the OD value and the volume resistance value are sufficiently high, so that it is a high-performance black matrix substrate.

(Production of color filter substrate)

Green pigment (PG36; 44g), yellow pigment (PY138; 19g), polyglycine A-2 (47g) and γ-butyrolactone (890g) were added to the storage tank, using a homomixer (special machine The mixture was stirred for 1 hour to obtain a G pigment predispersion G1. Then, 85% of Dano mill KDL (manufactured by SHINMARU ENTERPRISES) filled with 0.40 mmφ zirconia beads (Toray ceram beads; manufactured by Toray Co., Ltd.) The predispersion liquid G1 was supplied and dispersed at a number of revolutions of 11 m/s for 3 hours to obtain a G pigment dispersion liquid G1 having a solid content concentration of 7 mass% and a pigment/polymer (mass ratio) of 90/10. The G pigment dispersion G1 was diluted with polyamine acid A-2 and a solvent to obtain a green resin composition.

Add red pigment (PR254; 63g) instead of green pigment and yellow pigment to In the same manner, an R pigment dispersion liquid R1 having a solid content concentration of 7 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.

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

Each of the examples 1 to 11 and the comparative examples 1 and 3 On the black matrix substrate, a red paste was applied so as to have a film thickness after drying of 2.0 μm, and prebaked to form a polyimine precursor red colored film. Using a positive photoresist, red pixels are formed by the same method as above, and heated to 290 ° C And it is thermally hardened. The green paste was applied in the same manner to form green pixels, and the mixture was heated to 290 ° C to be thermally hardened. The blue paste was applied in the same manner to form blue crystals, and heated to 290 ° C to be thermally hardened.

(Production of liquid crystal display device)

Each of the obtained color filter substrates was washed with a neutral detergent, and then an alignment film containing a 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 heated polyimide film of the polyimide film was 0.07 μm. Thereafter, each color filter substrate was subjected to rubbing treatment, and the 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 the alignment film was applied and heated. Thereafter, a spherical separator having a diameter of 5.5 μm was spread, and each of the color filter substrates coated with the sealant was placed on the TFT substrate, and heated in an oven at 160 ° C for 90 minutes to seal. The agent hardens to obtain a unit cell. Each unit cell was allowed to stand at a temperature of 120 ° C under a pressure of 13.3 Pa for 4 hours, and then placed in nitrogen for 0.5 hour, and then the liquid crystal compound was again filled under vacuum. The filling of the liquid crystal compound is carried out by placing the unit cell in a chamber, and reducing the pressure to a pressure of 13.3 Pa at room temperature, then immersing the liquid crystal injection port in the liquid crystal, and recovering it with nitrogen gas. Pressure. After the liquid crystal is filled, the liquid crystal injection port is sealed by an ultraviolet curing resin. Next, the polarizing plate is attached to the outside of the two glass substrates of the unit cells, thereby completing the unit cells. Further, the obtained unit cell module is made to complete the liquid crystal display device.

Observing the obtained liquid crystal display device, the results were as follows: Example 1 to implementation In the liquid crystal display device of the black matrix substrate obtained in Example 9 and Example 11, since both the reflection chromaticity and the reflectance were low, the display characteristics were good even when external light was irradiated. The liquid crystal display device including the black matrix substrate obtained in Example 10 was generally excellent, but the pattern of the black matrix was shifted, so that it was slightly dim. On the other hand, in the liquid crystal display device including the black matrix substrate obtained in Comparative Example 1 and Comparative Example 3, since both the reflection chromaticity and the reflectance are high, when the external light is irradiated, the black display is observed. The display quality is 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 an 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‧‧‧Lighting layer (A)

22‧‧‧Lighting layer (B)

Claims (10)

A black matrix substrate comprising a transparent substrate, a light shielding layer (A) and a light shielding layer (B) in sequence, and an optical density per unit thickness of the light shielding layer (A) is lower than a thickness per unit thickness of the light shielding layer (B) The optical density, the light-shielding layer (A) contains a light-shielding material and fine particles having a refractive index of 1.4 to 1.8. The black matrix substrate according to claim 1, wherein the microparticles having a refractive index of 1.4 to 1.8 are selected from the group consisting of alumina, cerium oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, and More than one type of microparticles in a group consisting of sodium metasilicate. The black matrix substrate according to the first or second aspect of the invention, wherein the fine particles having a refractive index of 1.4 to 1.8 have a whiteness of 30% or more as measured by a method according to JIS P8148 (2001). The black matrix substrate according to any one of claims 1 to 3, wherein the transparent substrate comprises a polyimide resin. A color filter substrate, wherein the light shielding layer (A) and the light shielding layer (B) of the black matrix substrate according to any one of claims 1 to 4 have a pattern shape and no pattern exists. There are colored pixels in the part. A light-emitting device comprising the color filter substrate and the light-emitting element according to claim 5 of the patent application. The light-emitting device according to claim 6, wherein the light-emitting element is an organic electroluminescence element. A liquid crystal display device comprising, in order, a color filter substrate, a liquid crystal compound, and an opposite substrate according to claim 5 of the patent application. A method of manufacturing a black matrix substrate, which is a method of manufacturing a black matrix substrate according to any one of claims 1 to 4, further comprising the step of forming a light-shielding material over the transparent substrate And a step of forming a layer of the composition of the fine particles having a refractive index of 1.4 to 1.8; forming a layer of the photosensitive resin composition containing the light-shielding material thereon; performing pattern exposure by using a developing solution or a solvent to the above two layers The step of pattern processing. A method of manufacturing a color filter comprising the step of disposing a pixel in a portion where no pattern is present after the black matrix substrate is manufactured by the method of claim 9 of the patent application.