JPWO2014136738A1 - Black matrix substrate - Google Patents

Abstract

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

Description

  The present invention relates to a black matrix substrate that 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 sandwiched between two substrates, and expresses light and dark using the electro-optic response of the liquid crystal layer, but color display is also possible by using a color filter substrate It is.

  Conventionally, the black matrix that is formed on the color filter substrate and serves as the light shielding layer has been mainly a metal thin film made of a chromium-based material. However, in order to reduce cost and environmental pollution, a resin black matrix containing a resin and a light shielding material. Has been developed. A liquid crystal display device equipped with a color filter substrate having a resin black matrix containing a light-shielding material such as carbon black has excellent indoor visibility, but when used outdoors, it reflects external light derived from the black matrix. Deterioration of visibility due to the problem has been a problem.

  From such a background, various studies have been made to realize a resin black matrix having a high optical density (hereinafter sometimes referred to as “OD value”) and a low reflectance when viewed from the transparent substrate side. ing. For example, a method of using black colorant fine particles whose surface is coated with an insulating material (Patent Document 1), a method of adding carbon black to titanium oxynitride (Patent Document 2), a mixture of titanium nitride and titanium carbide. Method to be used (Patent Document 3), method having a two-layer structure of a colored relief layer and a black relief layer (Patent Document 4), and two layers of a light absorbing layer and a reflected light absorbing layer containing shape anisotropic metal fine particles A method (Patent Document 5) is proposed.

JP 2001-183511 A JP 2006-209102 A JP 2010-95716 A JP-A-8-146410 JP 2006-251237 A

  However, since a highly light-shielding material has a high reflectance in principle, it has been extremely difficult to achieve both a sufficient optical density and a low reflectance in the resin black matrix. Furthermore, the method of forming the resin black matrix with two layers also has a problem that it is difficult to achieve a low reflectance over the entire visible light region, and high conductivity is achieved by using metal fine particles. Thus, a display defect due to an electric field abnormality may occur.

  Accordingly, an object of the present invention is to provide a black matrix substrate on which a resin black matrix is formed, which has a sufficient optical density, has a low reflectance, and has a high resistance value and high reliability. To do.

The present invention provides the following black matrix substrate and the like.
(1) In order, it has a transparent substrate, a light shielding layer (A), and a light shielding layer (B),
The optical density per thickness of the light shielding layer (A) is lower than the optical density per thickness of the light shielding layer (B), and the light shielding layer (A) contains a light shielding material and fine particles having a refractive index of 1.4 to 1.8. A black matrix substrate.

The present invention provides the following black matrix substrate as a preferred embodiment of the above invention.
(2) The fine particles having a refractive index of 1.4 to 1.8 are selected from the group consisting of aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, and sodium metasilicate. The black matrix substrate which is fine particles of seeds or more.
(3) Any of the black matrix substrates (4), wherein the fine particles having a refractive index of 1.4 to 1.8 have a whiteness measured by a method according to JIS P8148 (2001) of 30% or more. Any of the black matrix substrates made of polyimide resin.

The present invention also provides the following using the above black matrix substrate.
(5) A color in which the light shielding layer (A) and the light shielding layer (B) of any one of the black matrix substrates have a pattern shape, and a colored pixel is present in a portion where no pattern exists. Filter substrate.
(6) A light emitting device having the color filter substrate and a light emitting element.
(7) The light emitting device, wherein the light emitting element is an organic EL element.
(8) A liquid crystal display device having the color filter substrate, a liquid crystal compound, and a counter substrate.

In addition, the present invention provides a preferable method for manufacturing the black matrix substrate and the color filter as follows.
(9) Above the transparent substrate,
Forming a layer of a composition containing a light shielding material and a resin,
A step of forming a photosensitive resin composition layer containing a light-shielding material thereon;
A method for producing a black matrix substrate, comprising performing a pattern exposure and patterning the two layers with a developer or a solvent.
(10) A method for producing a color filter, which comprises a step of providing a pixel where a pattern does not exist after producing a black matrix substrate by the above method.

  According to the black matrix substrate of the present invention, the light-shielding layer can realize sufficient light-shielding properties so as not to transmit the light of the backlight, and not only a high-contrast and clear image is obtained, but also the reflectance is low. It is possible to obtain a liquid crystal display device which is extremely excellent in visibility even under external light and has high electrical reliability.

It is a schematic sectional drawing which shows some embodiment of the black matrix substrate of this invention. It is a schematic sectional drawing which shows one Embodiment of the black matrix substrate of this invention. It is a schematic sectional drawing which shows one Embodiment of the light-emitting device of this invention.

  The black matrix substrate of the present invention has, in order, a light shielding layer (A) and a light shielding layer (B) formed on a transparent substrate, and the optical density per thickness of the light shielding layer (A) is the light shielding layer (B). ), 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, a resin black matrix (hereinafter referred to as “resin BM”) has a higher reflectivity as the optical density per unit thickness (a value obtained by dividing the optical density by thickness; hereinafter referred to as “OD / T”) increases. It is known to be higher. This is due to the following reason.

  In general, when two kinds of opposed colorless and transparent substances are in contact with each other, the reflectance R of light incident on the interface can be expressed by a difference in refractive index as shown in the following formula (1).

Reflectivity R = (n ₁ −n ₂ ) ² / (n ₁ + n ₂ ) ² (1)
(Here, n ₁ and n ₂ represent the refractive indexes of arbitrary colorless and transparent substances n ₁ and n ₂ , respectively)
On the other hand, in the case of a material that is not colorless and transparent, such as metal, the refractive index must be expressed by a complex refractive index,
A complex refractive index N = n−iκ (n represents a real part of the refractive index of the substance n, and κ represents an extinction coefficient) is used. When the colorless and transparent substance m is in contact with the non-colorless and transparent substance n, the reflectance R of light perpendicularly incident on the interface from the substance m side can be expressed by the following formula (2).

Reflectance R = {(mn) ² + κ ² } / {(m + n) ² + κ ² } (2)
(Where m represents the refractive index of the colorless and 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 Equation (2), it can be seen that the reflectance increases as the extinction coefficient κ increases. If the extinction coefficient κ is 0, that is, the substance n is colorless and transparent, the result is the same as that in the formula (1).
By the way, the extinction coefficient is proportional to the extinction coefficient α at a certain wavelength. Further, the extinction coefficient α can be approximated to a value obtained by multiplying OD / T by a constant. In other words, the extinction coefficient κ is proportional to the value of OD / T, and using equation (2), in principle, the higher the OD / T, the higher the reflectance R at the interface between the substance m and the substance n. I understand that

  The present inventors applied the substance m in the above formula (2) to the transparent substrate and the substance n to the resin BM, and the low reflectance and high light-shielding properties required as the characteristics of the resin BM are obtained under certain film thickness conditions. It was estimated that there was a trade-off relationship. In order to reduce reflection, it is effective to reduce OD / T. In this case, however, it is necessary to increase the thickness of the black matrix in order to ensure sufficient light shielding properties. A black matrix having a large film thickness causes a disorder in the alignment of the liquid crystal and lowers the contrast. Therefore, as a result of intensive studies to solve this trade-off, a layer having a small OD / T above the transparent substrate, that is, a light-shielding layer (A) that can be said to be a low optical density layer, and OD / T are less than the light-shielding layer (A). It came to be considered that a black matrix substrate having a large layer, that is, a light shielding layer (B) which can be said to be a high optical density layer in this order is suitable for solving the problem. The “light-shielding layer” here is not limited to the one that blocks light by 100%. According to the configuration of this black matrix substrate, since the light shielding layer (A) has a relatively low OD / T, the light coming from the transparent substrate side is at the interface of the light shielding layer (A) on the transparent substrate side. The reflection of is reduced. Since light attenuates in the light shielding layer (A), the amount of light reflected at the interface of the light shielding layer (B) on the light shielding layer (A) side is also reduced. As a result, the black matrix substrate of the present invention has a low reflectance. Further, since the light shielding layer (B) is provided, the light transmitted through the light shielding layer (B) can have sufficient light shielding properties. That is, it is assumed that such a configuration of the black matrix substrate can achieve both low reflection and sufficient light shielding properties for light coming from the transparent substrate side.

  However, according to the study by the present inventors, the light having entered from the transparent substrate side passes through the layer having a small OD / T, and the layer having a large OD / T has a small OD / T only with the above configuration. It has been found that there is reflection at the interface on the layer side, and it is not easy to achieve low reflection of the desired resin BM. Therefore, the inventors of the present invention, in the black matrix substrate having such a configuration, the layer having a small OD / T contains a light shielding material and fine particles having a refractive index of 1.4 to 1.8, thereby providing sufficient light shielding. And the present invention has been completed.

The light shielding layer (A) of the present invention has a layer structure in which the optical density is not 0 and is not substantially transparent, 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 0 and is not substantially transparent. The OD value referred to in the present invention is OD value = log ₁₀ (I ₀ / I) in the wavelength range of 380 to 700 nm.
I ₀ : Incident light intensity I: An average value of values obtained in steps of 5 nm using the transmitted light intensity is adopted.

<< Light shielding layer (A) >>
<Optical density>
The OD / T of the light shielding layer (A) is preferably 0.5 μm ⁻¹ or more, more preferably 1 μm ⁻¹ or more. Further, this value is preferably 3 μm ⁻¹ or less, more preferably 2.5 μm ⁻¹ or less. If this value is too small, the film thickness of the laminated resin BM must be increased in order to obtain a desired OD value. If this value is too large, the reflectance tends to increase. The OD / T of the light shielding layer (B) is preferably 3 μm ⁻¹ or more, more preferably 3.5 μm ⁻¹ or more. Further, it is preferably 8 μm ⁻¹ or less, more preferably 6 μm ⁻¹ or less. If this value is too small, the film thickness becomes too thick for the resin BM to obtain a desired OD value, and if it is large, the amount of light shielding material to be added must be increased, which may make pattern processing 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. Moreover, 6 or less, Furthermore 5 or less are more preferable. If the overall OD value is too low, part of the backlight light may be transmitted and the contrast may be lowered. On the other hand, if it is too high, not only the light-shielding layer (B) but also the amount of light-shielding material added to the light-shielding layer (A) must be increased, and the reflectance tends to increase when the desired film thickness is obtained.

The OD value of the light shielding layer (A) is preferably 0.5 or more, more preferably 0.8 or more, and is preferably 2.0 or less, more preferably 1.5 or less. The OD value of the light shielding layer (B) is more preferably 1.5 or more, further 2.0 or more, and on the other hand 5.0 or less, and further 3.5 or less.
<Fine particles>
The fine particles referred to in the present invention are preferably substantially uncolored and light, transparent or white. Black pigments and pigments such as red, blue, green, purple, yellow, magenta, and cyan are classified as light shielding materials described later.

Examples of the fine particle component include white ceramic particles or white pigments, various ceramics, and various resins. However, as described above, the refractive index needs to be 1.4 to 1.8.
The refractive index of fine particles here is the refractive index in visible light, and the value of the refractive index at a wavelength of 589 nm corresponding to the sodium D line can be adopted as a representative value. As a measuring method of the refractive index, it can be measured by using a liquid immersion method, that is, a Becke line method, using a fine particle itself or a substance having the same composition as the fine particle as a sample. As a method of obtaining the refractive index by the Becke line method, prepare 30 samples of the same material of the target fine particles, measure the refractive index of each one, and calculate the refractive index from the average value thereof. Can do.

The refractive index of the fine particles used in the present invention is required to be 1.4 to 1.8, but is preferably 1.5 to 1.7. A low refractive index means that the density of substances constituting the fine particles is reduced in principle. Therefore, there is a problem that such low density particles are easily attacked by an organic solvent used as a dispersion medium when forming a light shielding layer. Further, the solvent resistance of the completed black matrix substrate becomes insufficient. On the other hand, if the refractive index is too high, the refractive index of the light shielding layer (A) becomes too large compared to the transparent substrate, so that reflection on the surface of the light shielding layer (A) on the transparent substrate side becomes large, resulting in black The reflection of the matrix substrate tends to increase. According to the configuration of the present invention, the fine particles having a refractive index in the above range are dispersed in a layer having a small OD / T, so that the influence of incident light scattered by the fine particles is minimized and the OD / T is reduced. The refractive index of the small layer can be set to a value close to that of the transparent substrate, and it is presumed that the reflected light attenuates in combination with the light shielding effect of the light shielding material.
Specific examples of the fine particles having a refractive index of 1.4 to 1.8 include resin fine particles such as acrylic resin, polyethylene resin, silicone fine particles, and fluorine resin. Commercially available acrylic resin fine particles, such as Nippon Paint FS-101, FS102, FS106, FS-107, FS-201, FS-301, FS-501, FS-701, MG-155E, MG-451, MG- 351, “Tough Tick” (registered trademark) F-120 and F-167 manufactured by Toyobo.

  As described above, the fine particles that can be used in the present invention are not substantially colored, are preferably pale, transparent or white, and are preferably white. Examples of those having a refractive index of 1.4 to 1.8 include minerals such as talc, mica or kaolin clay, oxides such as alumina (aluminum oxide) or silica (silicon oxide), barium sulfate or calcium sulfate, etc. Sulfate, barium carbonate, calcium carbonate, carbonate such as magnesium carbonate or strontium carbonate, sodium metasilicate or sodium stearate, but from the viewpoint of electrical reliability, aluminum oxide, silicon oxide, barium sulfate, sulfuric acid A substance selected from the group consisting of calcium, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate and sodium metasilicate is preferable, and barium sulfate is more preferable. Examples of commercially available barium sulfate include “BARIFINE” (registered trademark) BF-10, BF-1, BF-20, or BF-40 (all of which are manufactured by Sakai Chemical Industry Co., Ltd.). The fine particles having a refractive index of 1.4 to 1.8 of the present invention preferably have a whiteness measured by a method according to JIS P8148 (2001) of 30% or more, and more preferably 50% or more. In the measurement of the whiteness of the fine particles, the measurement is performed by sufficiently filling the fine particles in a measurement container so that the whiteness becomes a constant value. The fine particles shown in this paragraph have a whiteness of 30% or more.

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

  The particle diameter of the fine particles is preferably 1 μm or less, preferably 5 to 500 nm, and more preferably 10 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, light scattering tends to increase and the reflectance tends to increase. Here, the particle size of the fine particles refers to the primary particle size of the fine particles. The primary particle diameter of the fine particles can be calculated by observing the primary particle diameter of 100 randomly selected fine particles with an electron microscope and determining the average value. When the shape is other than spherical, the average value of the maximum width and the minimum width observed with an electron microscope is calculated as the primary particle diameter of one particle, and the average value of 100 primary particle diameters is calculated. Can be calculated by obtaining. The fine particles having the particle diameter as described above are preferably contained in 90% by mass or more of the fine particles contained in the low optical density layer.

Examples of the method for producing fine particles include a pulverization method in which a material such as a mineral as a raw material is pulverized and refined, a chemical method in a gas phase, a liquid phase, or a solid layer, or a physical method. Examples of the pulverization method include a jet method, a hammer method, and a mill method. Examples of the chemical method in the gas phase include a chemical vapor deposition method (CVD method), an electric furnace method, a chemical flame method, and a plasma method. Examples of the chemical method in the liquid phase include a precipitation method, an alkoxide method, and a hydrothermal method. Examples of the chemical method in the solid phase include a crystallization method. Examples of the physical method include a spray method, a solution combustion method, and a lyophilization method. Among these, the precipitation method is preferable because the particle size of the fine particles can be easily controlled.
<Composition of light shielding layer (A)>
The light shielding layer (A) in the black matrix substrate of the present invention contains a light shielding material and fine particles having a refractive index of 1.4 to 1.8, and preferably further 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, and aniline black. Examples of the mixed color organic pigment include those obtained by mixing pigments such as red, blue, green, purple, yellow, magenta, and cyan into a pseudo black color. Examples of the inorganic pigment include graphite. Other examples include fine metal particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver. In addition, oxides, composite oxides, sulfides, nitrides and carbides of the metals described above can be given. Titanium oxynitride obtained by nitrogen reduction of titanium oxide, that is, at least one selected from titanium black, titanium nitride, titanium carbide, and carbon black is preferable. Of these, titanium oxynitride is more preferable.

Here, titanium oxynitride refers to a compound represented by TiN _x O _y (0 <x <2.0, 0.1 <y <2.0). Since it falls, it is preferable that x / y is 0.1-10, and it is more preferable that it is 1-3.

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

  The ratio of the light shielding material in the light shielding layer (A) is preferably 5% by mass or more, and more preferably 10% by mass or more. Further, the ratio is preferably 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, if the ratio of the light shielding material is large, patterning of the light shielding layer (A) may be difficult.

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

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

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

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

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

  In order to improve the heat resistance and insulation of the polyimide resin, the diamine compound used for obtaining the polyamic acid is preferably an aromatic diamine compound, and the compound having an acid anhydride group is preferably acid dianhydride.

  Examples of the aromatic diamine compound include paraphenylene diamine, metaphenylene diamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-bis (4-aminophenoxy) benzene, 2,2-bis (trifluoromethyl) benzidine, 9,9'-bis (4-aminophenyl) fluorene 4,4'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 3,3′-di Minodiphenylamine, 2,4'-diaminodiphenylamine, 4,4'-diaminodibenzylamine, 2,2'-diaminodibenzylamine, 3,4'-diaminodibenzylamine, 3,3'-diaminodibenzylamine N, N′-bis- (4-amino-3-methylphenyl) ethylenediamine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide, 4,3 '-Diaminobenzanilide, 2,4'-diaminobenzanilide, N, N'-p-phenylenebis-p-aminobenzamide, N, N'-p-phenylenebis-m-aminobenzamide, N, N'- m-phenylenebis-p-aminobenzamide, N, N′-m-phenylenebis-m-aminobenzamide, N, N ′ Dimethyl-N, N′-p-phenylenebis-p-aminobenzamide, N, N′-dimethyl-N, N′-p-phenylenebis-m-aminobenzamide, N, N′-diphenyl-N, N ′ -P-phenylenebis-p-aminobenzamide or N, N'-diphenyl-N, N'-p-phenylenebis-m-aminobenzamide, but paraphenylenediamine, metaphenylenediamine, 3,3'- Diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 9,9′-bis (4-aminophenyl) fluorene Alternatively, 4,4′-diaminobenzanilide is preferable.

  Examples of the aromatic tetracarboxylic acid include 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4, 9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1 , 2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-paraterphenyltetracarboxylic dianhydride or 3,3 ′, 4,4′-metaterphenyltetracarboxylic Examples thereof include acid dianhydrides, and 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-benzophenone tetracarboxylic dianhydride or pyromellitic dianhydride is preferable. When a fluorine-based tetracarboxylic dianhydride such as 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride is used, a polyimide having good transparency in a short wavelength region can be obtained. .

  In addition polymerization of a compound having an acid anhydride group and a diamine compound to obtain a polyamic acid, an acid anhydride such as maleic anhydride or phthalic anhydride may be added as a terminal blocking agent as necessary. I do not care. Moreover, in order to improve adhesiveness with inorganic substances, such as a glass plate or a silicon wafer, you may use the acid anhydride which has a silicon atom, or the diamine compound which has a silicon atom. As the diamine having a silicon atom, a siloxane diamine compound such as bis-3- (aminopropyl) tetramethylsiloxane is preferable. As for the ratio of the diamine which has a silicon atom in all the diamine compounds, 1-20 mol% is preferable. When there are few siloxane diamine compounds, the adhesive improvement effect cannot be acquired. On the other hand, if it is too large, the heat resistance of the film tends to decrease. The pattern formation of the light-shielding layer may be performed with an alkaline solution. However, if the amount is too large, the adhesion may be excessively high, which may cause a problem of a residual film during alkali development.

  As a compound having an acid anhydride group and a diamine compound for obtaining a polyamic acid, an alicyclic acid dianhydride or an alicyclic diamine may be used. Examples of the alicyclic acid dianhydride or alicyclic diamine include 1,2,4,5-cyclohexanetetracarboxylic dianhydride and bicyclo [2.2.2] oct-7-ene-2. , 3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic Acid 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-dimethananaphthalene tetracarboxylic dianhydride or bis [2- (3-aminopropoxy) ethyl] ether, 4-Butanediol-bis (3-a Nopropyl) ether, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis (2-aminoethoxy) ethane, 1,2 -Bis (3-aminopropoxy) ethane, triethylene glycol-bis (3-aminopropyl) ether, polyethylene glycol-bis (3-aminopropyl) ether, 3,9-bis (3-aminopropyl) -2,4 , 8,10-tetraspiro-5,5-undecane or 1,4-butanediol-bis (3-aminopropyl) ether.

  The light shielding layer (A) may contain, as other additives, an adhesion improver, a polymer dispersant or a surfactant. Examples of the adhesion improving agent include a silane coupling agent or a titanium coupling agent. The adhesion improver is preferably added in an amount of 0.2 to 20% by mass with respect to a 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 generally added in an amount of 1 to 40% by mass with respect to the light shielding material. Examples of the surfactant include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine, a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride, lauryldimethylamine oxide, or lauryl. Amphoteric surfactants such as carboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate, and silicone-based interfaces mainly composed of polydimethylsiloxane An activator or a fluorosurfactant is mentioned. The surfactant is generally added in an amount of 0.001 to 10% by mass with respect to the pigment, but is preferably added in an amount of 0.01 to 1% by mass. If the amount of the surfactant is small, the coatability, the smoothness of the colored coating, or the Benard cell prevention effect may be insufficient. On the other hand, if the surfactant is too much, the physical properties of the coating film may be poor. The various additives described above are included in the composition when the light shielding layer (A) is provided, but may then be incorporated into the chemical structure of the resin by chemical reaction with the resin by heating or light irradiation.

<< 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 more preferably contains a resin.

The light shielding material contained in the light shielding layer (B) is the same as that of the light shielding layer (A), but is selected from carbon black, titanium oxynitride, titanium nitride and titanium carbide because of its large OD / T. One or more are preferable, and titanium nitride or titanium nitride is more preferable. Here, the titanium nitride means a substance containing titanium nitride as a main component and titanium oxide TiO ₂ , low-order titanium oxide TinO _2n-1 (1 ≦ n ≦ 20) or titanium oxynitride as a subcomponent. The titanium nitride particles contain oxygen atoms, but in order to obtain a higher OD / T, it is preferable that the number of oxygen atoms is small, the content of oxygen atoms is more preferably 12% by mass or less, and 8% by mass or less. Further preferred.

  Examples of the synthesis of titanium nitride particles include a gas phase reaction method such as an electric furnace method or a thermal plasma method. Among them, the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle diameter, and has high productivity. Examples of the method for generating thermal plasma include direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, and hybrid plasma. Among these, high-frequency plasma is preferable because there is little mixing of impurities from the electrodes.

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

  The proportion of the light shielding material in the light shielding layer (B) is preferably 10% by mass or more, and more preferably 40% by mass or more. The proportion is preferably 90% by mass or less, 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 too much, patterning becomes difficult.

  The proportion of the resin that can be contained in the light shielding layer (B) is preferably 10% by mass or more, and more preferably 20% by mass or more. Further, the ratio is preferably 90% by mass or less, and more preferably 60% by mass or less.

  Examples of the resin that can be contained in the light shielding layer (B) include the same resins as those contained in the light shielding layer (A), and among them, acrylic resins are preferable.

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

  Examples of the unsaturated carboxylic acid used as a raw material for the copolymer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid. Examples of the ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, and n-acrylate. Butyl, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, Examples include unsaturated carboxylic acid alkyl esters such as n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate or benzyl methacrylate. Other ethylenically unsaturated compounds include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene. Other examples include unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate or glycidyl methacrylate, and carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate. It can also be grafted by copolymerizing an oligomer or polymer having an unsaturated group at the terminal as a macromonomer, for example, a vinyl cyanide compound such as acrylonitrile, methacrylonitrile or α-chloroacrylonitrile, 1, 3 -An aliphatic conjugated diene such as butadiene or isoprene, polystyrene having an acryloyl group or a methacryloyl group at each end, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate or polybutyl methacrylate can be used. Among these copolymer components, a copolymer of 2 to 4 components of a monomer selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene is preferable. In general, a developing operation is performed when patterning the resin BM. In order to make the dissolution rate in a commonly used alkaline developer appropriate, the weight average molecular weight Mw (measured by gel permeation chromatography at a temperature of 23 ° C. using tetrahydrofuran as a carrier, and using a standard polystyrene calibration curve) And the acid value is more preferably 70 to 150 (mgKOH / g).

  Moreover, the acrylic resin which has an ethylenically unsaturated group in a side chain can be contained in the step of the raw material of a light shielding layer (B). By containing this material, the sensitivity in exposure and development when patterning the resin BM can be improved. As the ethylenically unsaturated group, an acryl group or a methacryl group is preferable. The acrylic resin having an ethylenically unsaturated group in the side chain can be obtained by addition-reacting an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to the carboxyl group of the acrylic resin having a carboxyl group.

  Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include cyclomer (registered trademark) P (Daicel Chemical Industries, Ltd.) or alkali-soluble cardo resin, which is a commercially available acrylic resin. In order to make the solubility in a solvent or an alkali developer appropriate, it is preferable that the weight average molecular weight (Mw) is 2,000 to 100,000 and the acid value is 70 to 150 (mgKOH / g).

  A polyfunctional acrylic monomer or a reaction product thereof can be further contained in the raw material of the light shielding layer (B). The light shielding layer is patterned later, but the processing is generally performed in the order of pattern exposure and development. The compound is polymerized and cross-linked by exposure, and becomes insoluble in the developer. Examples of the polyfunctional acrylic monomer include polyfunctional acrylic monomers or oligomers. Examples of the polyfunctional acrylic monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid Ester, Propylene oxide phthalate (meth) acrylate, Trimellitic acid diethylene glycol (meth) acrylate, Rosin modified epoxy di (meth) acrylate, Alkyd modified (meth) acrylate, Full orange acrylate oligomer, Tripropylene glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylol propylene 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-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] Sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4,4′-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4 − 3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4 -(3-Acryloxy-2-hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full orange acrylate and biscresol full orange methacrylate.

  These polyfunctional monomers or oligomers can be appropriately selected and combined, a compound having a functional group of 3 or more is preferable, a compound having a functional group of 5 or more is more preferable, and dipentaerythritol hexa (meth) acrylate or dipenta More preferred is erythritol penta (meth) acrylate.

  Since the light-shielding layer (B) tends to absorb not only the visible light region but also ultraviolet rays effective for photocrosslinking, the light-shielding layer (B) is preferably a combination of polyfunctional acrylic monomers that can be cured with high sensitivity even with a small amount of ultraviolet rays. Specifically, in addition to dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate, (meth) acrylate having a fluorene ring that has a lot of aromatic rings and high water repellency in the molecule is used in combination. Is preferred. The (meth) acrylate having a fluorene ring is preferably used in an amount of 90 to 40 parts by mass with respect to 10 to 60 parts by mass of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  The raw material of the light shielding layer (B) can contain a photopolymerization initiator. For example, inorganic light such as benzophenone compound, acetophenone compound, oxanthone compound, imidazole compound, benzothiazole compound, benzoxazole compound, oxime ester compound, carbazole compound, triazine compound, phosphorus compound or titanate A polymerization initiator is mentioned.

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, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane "Irgacure" (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone), OXE01 (1,2-octanedione, 1- [4- (phenylthio)) -2- (O-ben Iloxime)]), CGI-113 (2- [4-methylbenzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butanone, t-butylanthraquinone) or CGI-242 (ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)) (all are manufactured by Ciba Specialty Chemicals), 1-chloro Anthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethyl Anthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenyl Midazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine or “ADEKA” (registered trademark) “Optomer” ”(Registered trademark) N-1818 or N-1919 and other carbazole compounds (all manufactured by Asahi Denka Kogyo Co., Ltd.). The raw material for the light-shielding layer (B) may contain, as other additives, an adhesion improver, a polymer dispersant, or a surfactant. Specifically, the same thing as what is contained in a light shielding layer (A) is mentioned.
<< Resin BM >>
The film 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, more preferably 1.0 μm or less. The total film thickness of the resin BM including both layers is preferably 0.5 μm or more, and more preferably 1.0 μm or more. The film thickness is preferably 2.0 μm or less, more preferably 1.5 μm or less. If the total film thickness is too small, an appropriate optical density may not be obtained. On the other hand, if it is too large, the contrast may decrease due to poor liquid crystal alignment.

  Examples of the pattern shape of the resin BM formed on the black matrix substrate of the present invention include a rectangular shape, a stripe shape, a square shape, a polygonal shape, a corrugated shape, and an uneven shape. The width of the pattern is preferably 3 to 30 μm, more preferably 3 to 10 μm, and further preferably 3 to 6 μm. If the pattern width is too large, the opening area of the pixel may be reduced and the luminance may be reduced. On the other hand, if the pattern width is too small, the pattern may be lost during processing.

  The pattern of the light shielding layer (A) and the pattern of the light shielding layer (B) constituting the black matrix substrate of the present invention are preferably substantially the same in order to maximize the aperture area of the pixel and improve the luminance. . Specifically, it is preferable that the pattern shapes of the light shielding layer (A) and the light shielding layer (B) such as a rectangle or a stripe are substantially the same. The pattern widths do not need to be exactly the same, but the difference between the pattern width of the light shielding layer (A) and the pattern width of the light shielding layer (B) is preferably 3 μm or less, more preferably 1 μm or less, and 0.5 μm or less. Is more preferable.

The surface resistance value (Ω / □) of the resin BM formed on the black matrix substrate of the present invention is preferably 10 ⁸ (Ω / □) or more, and more preferably 10 ¹⁵ (Ω / □) or more. By forming the resin BM having a large surface resistance value, the insulating property of the color filter substrate is increased, and the electric field is not disturbed when a voltage is applied, and the liquid crystal orientation is good, and as a result, the quality is good. A liquid crystal display device having an excellent display can be obtained.
<< Transparent substrate >>
Examples of the transparent substrate include quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as soda lime glass whose surface is coated with silica, or an organic plastic film or sheet, and a refractive index of 1.4 to 1. .8 is preferable, and 1.5 to 1.7 is more preferable. The term “transparent” as used herein means that the transmittance is 80% or more, preferably 90% or more, in the entire region having a wavelength of 380 to 700 nm.

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

  The polyimide resin film can be prepared by applying a polyimide precursor resin solution such as polyamic acid onto a temporary substrate, and then drying and heating.

  First, a polyimide precursor resin composition is applied on a temporary substrate. Examples of the material of the temporary substrate include silicon wafers, ceramics, gallium arsenide, soda lime glass, and alkali-free glass. Examples of the method for applying the polyimide precursor resin solution on the temporary substrate include a slit coating method, a spin coating method, a spray coating method, a roll coating method, and a bar coating method. Is preferred. Next, the temporary substrate coated with the polyimide precursor resin solution is dried to obtain a polyimide precursor resin composition film. Examples of the drying method include a method using a hot plate, an oven, an infrared ray, a vacuum chamber, or the like. When a hot plate is used, the temporary substrate is heated and dried on a hot plate or a jig such as a proxy pin installed on the hot plate. Next, the polyimide precursor resin composition film is heated at 180 to 400 ° C. to be converted into a polyimide resin film.

As a method of peeling this polyimide resin film from the temporary substrate, for example, a method of mechanical peeling, a method of immersing in a chemical solution or water such as hydrofluoric acid, or a laser irradiation to the interface between the polyimide resin film and the temporary substrate The method of doing is mentioned. In addition, it is possible to manufacture a black matrix substrate, a liquid crystal display device or a light-emitting device without peeling off the polyimide resin film from the temporary substrate, and then peel off the polyimide resin film from the temporary substrate, but from the viewpoint of dimensional stability. It is preferable to peel off the temporary filter substrate after manufacturing the color filter substrate or the like.
<< Method for Forming Light Shielding Layer (A) and Light Shielding Layer (B) >>
Examples of methods for forming the light shielding layer (A) and the light shielding layer (B) on the transparent substrate of the present invention include the following two methods.
1) Method of repeating photolithography process a plurality of times A non-patterned light shielding layer (A) is provided on a transparent substrate, and the layer is patterned. Thereafter, a light-shielding layer (B) that is not yet patterned is provided, and the layer is patterned.
As a method for patterning the light shielding layer (A), a photolithography method is exemplified. Examples thereof include a method in which a light shielding layer (A) is provided using a photosensitive resin composition, pattern exposure is performed, and development is performed to obtain a pattern. As another method, a light-shielding layer (A) is provided using a non-photosensitive resin composition. A photoresist is provided thereon, pattern exposure is performed, and development is performed to form a photoresist pattern. Simultaneously with the development, the light shielding layer (A) can also be patterned by etching with a developer using the photoresist pattern as a mask. Using the photoresist pattern after development as a mask, the light shielding layer (A) can also be patterned by etching with a solvent. The pattern of the light shielding layer (B) can also be formed in the same manner as the patterning method of the light shielding layer (A) described above.
2) Method of performing photolithography process once The light-shielding layer (A) that is not yet patterned is provided on the transparent substrate, and the light-shielding layer (B) that is not patterned is further provided. The layer (A) and the light shielding layer (B) are patterned. As a photolithography method, a photoresist is provided on the light shielding layer (B), pattern exposure is performed, and simultaneously with development of the photoresist, the light shielding layer (B) and the light shielding layer (A) are etched using the photoresist pattern as a mask. Then, a pattern is formed. Alternatively, after forming a photoresist pattern, the light shielding layer (A) and the light shielding layer (B) may be patterned with a solvent using the photoresist pattern as a mask. As another method for performing photolithography at once, an unpatterned light-shielding layer (A) is provided on a transparent substrate, and an unpatterned light-shielding layer made of a photosensitive resin composition ( B) is provided, and the light shielding layer (B) is patterned by photolithography, and the light shielding layer (A) is also patterned with a developer or a solvent. In this case, a photosensitive resin composition may be used for the light shielding layer (A).

  Details of the method for forming the pattern of the light shielding layer (A) and the light shielding layer (B) in the black matrix substrate will be described. A light shielding layer (A) is obtained by apply | coating to a transparent substrate by using a resin composition as a raw material. Examples of the method of applying the resin composition on the transparent substrate include a spin coater, a bar coater, a blade coater, a roll coater, a die coater, and a screen printing method. Other methods include a method of immersing the transparent substrate in the black resin composition and a method of spraying the black resin composition onto the substrate. In order to improve applicability, the resin composition may further contain a solvent. For example, esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide or N, N-dimethylformamide, or Lactones may be mentioned, but lactones or mixed solvents containing lactones as main components are preferable in order to enhance the dispersion effect of the pigment as a light shielding material. Here, the solvent containing lactones as a main component refers to a solvent having a maximum mass ratio of lactones in all solvents. Moreover, as a lactone, a C3-C12 aliphatic cyclic ester compound is preferable. Examples of lactones include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. Among these, γ-butyrolactone is preferable from the viewpoint of solubility of the polyimide precursor. Examples of solvents other than lactones include 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, and tripropylene. Examples include glycol monomethyl ether, propylene glycol mono tertiary butyl ether, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, methyl carbitol acetate, ethyl carbitol and ethyl carbitol acetate. The proportion of the solvent in the black resin composition used for forming the light shielding layer (A) is preferably from 70 to 98 mass%, more preferably from 80 to 95 mass%, from the viewpoints of coating properties and drying properties.

  Examples of the method for producing the resin composition used for forming the light shielding layer (A) include a method in which the light shielding material and the fine particles are directly dispersed in the resin solution using a disperser. As another method, there is a method of preparing a dispersion by dispersing a light shielding material and fine particles in water or an organic solvent using a disperser, and then mixing the dispersion and the resin solution. Examples of the method for dispersing the light shielding material and the fine particles include a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill. Among these, a bead mill is preferable from the viewpoint of dispersion efficiency and fine dispersion. Examples of the bead mill include a coball mill, a basket mill, a pin mill, and a dyno mill. As beads of the bead mill, for example, titania beads, zirconia beads, or zircon beads are preferable. The bead diameter used for dispersion is preferably 0.01 to 5.0 mm, and more preferably 0.03 to 1.0 mm. When the primary particle diameter of the pigment or the secondary particles formed by agglomeration of the primary particles is small, the bead diameter used for dispersion is preferably 0.03-0.10 mm fine dispersed beads. In this case, it is preferable to disperse using a bead mill having a separator by a centrifugal separation method capable of separating fine dispersed beads and a dispersion. On the other hand, when a light shielding material or fine particles containing coarse particles of about submicron are dispersed, dispersed beads having a bead diameter of 0.10 mm or more are preferable in order to obtain a sufficient crushing force. Further, the light shielding material and the fine particles may be dispersed separately. In this case, it is preferable to use the same solvent in order to prevent aggregation due to solvent shock.

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

  Next, in order to form the light shielding layer (B) on the dry film of the light shielding layer (A), a black composition for the light shielding layer (B) having an OD / T larger than that of the light shielding layer (A). Apply and dry.

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

  As the solvent contained in the photosensitive black resin composition used for forming the light shielding layer (B), water or an organic solvent is appropriately selected according to the dispersion stability of the dispersed light shielding material and the solubility of the resin component to be added. be able to. Examples of the organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, and lactone polar solvents. Examples of 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.), 2-ethylhexyl acetate (boiling point 199 ° C.), 2-butoxyethyl acetate (bp 192 ° C.), 3-methoxy-3-methyl-butyl acetate (bp 188 ° C.), diethyl oxalate (bp 185 ° C.), ethyl acetoacetate (bp 181 ° C.), cyclohexyl acetate (bp 174 ° C), 3-methoxy-butyl acetate (boiling point 173 ° C), methyl acetoacetate (boiling point 172 ° C), ethyl-3-ethoxypropionate (boiling point 170 ° C), 2-ethylbutyl acetate (boiling point 162 ° C), iso Pentylpropionate (boiling point 160 ° C), propylene glycol Glycol monomethyl ether propionate (boiling point 160 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), such as acetic acid pentyl (boiling point 0.99 ° C.) or propylene glycol monomethyl ether acetate (boiling point 146 ° C.) and the like.

  Examples of other solvents 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.). ), Monoethyl ether (boiling point 135 ° C.), methyl carbitol (boiling point 194 ° C.), ethyl carbitol (202 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene (Poly) alkylene glycol ether solvents such as glycol tertiary butyl ether (boiling point 153 ° C.) or dipropylene glycol monomethyl ether (boiling point 188 ° C.), ethyl acetate (boiling point 7 ° C), aliphatic esters such as butyl acetate (boiling point 126 ° C) or isopentyl acetate (boiling point 142 ° C), butanol (boiling point 118 ° C), 3-methyl-2-butanol (boiling point 112 ° C) or 3-methyl-3 -Aliphatic alcohols such as methoxybutanol (boiling point 174 ° C), ketones such as cyclopentanone or cyclohexanone, xylene (boiling point 144 ° C), ethylbenzene (boiling point 136 ° C) or solvent naphtha (petroleum fraction: boiling point 165 to 178) ° C).

Furthermore, since application by a die coating apparatus has become mainstream with an increase in the size of a transparent substrate, a solvent having a boiling point of 150 ° C. to 200 ° C. is 30 to 75% by mass in order to achieve appropriate volatility and drying properties. A mixed solvent is preferable.
As a manufacturing method of the photosensitive resin composition which can be used for formation of a light shielding layer (B), the method similar to a light shielding layer (A) is mentioned.
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 and dried thereon, and then the mask is formed. Then, ultraviolet light is irradiated from the exposure apparatus, and development is performed with, for example, an alkaline developer. As the alkaline developer, an aqueous solution of tetramethylammonium hydroxide or an aqueous solution of an alkali metal hydroxide can be used. For example, 0.01 to 1% by mass of a surfactant such as a nonionic surfactant can be added to the developer.

  The obtained pattern becomes the resin BM patterned by heat-processing after that. The heat treatment of the laminated pattern is preferably performed continuously or stepwise at 150 to 300 ° C. for 0.25 to 5 hours, for example, in air, nitrogen, or vacuum. The temperature of the heat treatment is more preferably 180 to 250 ° C.

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

Next, a preferable shape of the resin BM will be described. FIG. 1 is a schematic diagram showing some embodiments of the black matrix substrate of the present invention. The resin BM11 including the light shielding layer (A) having a small OD / T and the light shielding layer (B) having a large OD / T is patterned on the transparent substrate 10. The resin BM formed on the black matrix substrate of the present invention needs to have layers in order as shown in FIGS. 1 (a) to 1 (e). However, as shown in FIG. A mountain-shaped pattern as shown in FIG. 1B, an inverted mountain-shaped pattern as shown in FIG. 2C, and a pattern of the light-shielding layer (B) as shown in FIG. 2D are smaller than the light-shielding layer (A). However, as shown in FIG. 2E, the pattern of the light shielding layer (B) may be larger than that of the light shielding layer (A). In particular, in order to reduce the line width of the resin BM and improve the aperture ratio of the pixel, the light shielding layer (A) 21 and the light shielding layer (B) 22 are approximately as shown in FIGS. It is preferable that they have the same width, and it is more preferable that they are stacked in a mountain shape as shown in FIG. 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 11 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 L2. When the line width at the top of the light shielding layer (B) is L3, it is preferable to satisfy the relationship of L1>L2> L3 in order to improve visibility. Furthermore, the difference between L1 and L3 is preferably 3 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less.
<< Use of black matrix substrate >>
The black matrix substrate of the present invention can be used for electronic materials and various displays. Taking advantage of the high optical density and low light reflection characteristics of the black matrix substrate of the present invention, light-shielded images such as plasma display panel (PDP) partition walls, dielectric patterns, electrode (conductor circuit) patterns, or electronic component wiring patterns Can be used to fabricate. Among them, in order to improve the display characteristics of a color filter used in a color liquid crystal display device or the like, the resin BM is suitable as a black matrix substrate provided on the interval portion and the peripheral portion of the colored pattern, the outside light side of the TFT, and the like.
<Color filter>
The color filter substrate disclosed in the present invention is such that colored pixels such as red, green, and blue are formed in a portion where the resin BM pattern that is a light shielding layer does not exist using the black matrix substrate of the present invention. It is.

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

  As the pigment dispersed in the pixels of the color filter substrate of the present invention, those excellent in light resistance, heat resistance and chemical resistance are preferable.

  Examples of the red pigment include Pigment Red (hereinafter “PR”) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR190, PR192, PR209, PR215, PR216, Examples include PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, and PR254.

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

  Examples of the yellow pigment include pigment yellow (hereinafter referred to as “PY”) PY12, PY13, PY14, PY17, PY20, PY24, PY83, PY86, PY93, PY94, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY173, PY180 or PY185.

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

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

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

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

  When the pixel of the color filter substrate of the present invention is a colored resin film in which a pigment is dispersed, examples of the binder resin used for the formation include acrylic resin, polyvinyl alcohol, polyamide, and polyimide. From the viewpoint of chemical properties, polyimide is preferable.

The color filter substrate of the present invention may form a fixed spacer. The fixed spacer refers to a spacer that is fixed at a specific location on the color filter substrate and contacts the counter substrate when a liquid crystal display device is manufactured. Thus, a certain gap is maintained between the counter substrate and the liquid crystal compound is filled between the gaps. By forming the fixed spacer, it is possible to omit the step of dispersing the spherical spacer in the manufacturing process of the liquid crystal display device and the step of kneading the rod-shaped spacer in the sealing agent.
<Liquid crystal display device, light emitting device>
The liquid crystal display device of the present invention has the color filter substrate, the liquid crystal compound and the counter substrate in this order.
The light-emitting device of the present invention is characterized in that the color filter substrate of the present invention and a light-emitting element are bonded together.

  As the light emitting element, an organic EL element is preferable. The light-emitting device of the present invention makes use of the feature that the black matrix substrate has high OD and low reflection, effectively shields excess light from the light-emitting element in black display, suppresses reflection of external light, and contrast. High and clear display can be obtained.

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

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

  The color filter substrate 20 is composed of a black matrix substrate manufactured by the manufacturing method of the present invention, red, green or blue pixels 23 to 25 formed in the openings, and an overcoat layer 26. Here, the black matrix substrate included in the color filter substrate 20 includes the substrate 10 and the resin BM11 in which the light shielding layer (A) 21 and the light shielding layer (B) 22 are laminated.

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

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

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

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

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

  The light of the organic EL layer 29 is preferably white light. By appropriately changing the color of the pixels 23 to 25 of the color filter substrate 20 according to the wavelength distribution of white light, a light emitting device having a desired color reproduction range can be realized.

  Examples of the material for the light emitting layer include cyclopentamine, tetraphenylbutadiene, triphenylamine, oxadiazol, pyrazoloquinoline, distyrylbenzene, distyrylarylene, silole, thiophene, pyridine, perinone, perylene, oligothiophene, and Examples thereof include organic compounds having a skeleton such as trifumanylamine, and pigment materials such as oxadiazole dimer and pyrazoline dimer. Moreover, an aluminum quinolinol complex, a benzoquinolinol beryllium complex, a benzoxazole zinc complex, a benzothiazole zinc complex, an azomethylzinc complex, a porphyrin zinc complex, and a europium complex are mentioned. A metal complex having a rare earth metal such as Al, Zn, Be, Tb, Eu or Dy as the central metal and an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole or quinoline structure as the ligand, etc. Examples include metal complex materials. Examples thereof include high molecular weight materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, and polyvinylcarbazole derivatives. The thickness of the light emitting layer is usually 0.05 to 5 μm, and can be formed by, for example, a vapor deposition method, a spin coating method, a printing method, or an ink jet method.

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

  Examples of the material of the extraction electrode 33 include silver, aluminum, gold, chromium, nickel, and molybdenum.

  Furthermore, a flexible light emitting device can be obtained by bonding a flexible color filter substrate using a polyimide resin film as a substrate and a light emitting element. And a flexible organic EL display can be manufactured by bonding the above-described flexible color filter substrate and the organic EL element which is a light emitting element.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these.

<Evaluation method>
[Refractive index of fine particles]
The refractive index was determined by the Becke line method. Thirty samples of the same substance of the target fine particles were prepared, the refractive index was measured one by one, and the refractive index was calculated from the average value thereof.

[Optical density (OD value)]
A light shielding layer having a predetermined thickness is formed on a non-alkali glass having a thickness of 0.7 mm, and the intensity of each of incident light and transmitted light is measured using a microspectroscope (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.). 7), and an average value of values obtained in increments of 5 nm in a wavelength range of 380 to 700 nm.
OD value = log ₁₀ (I ₀ / I) (7)
I ₀ : Incident light intensity I: Transmitted light intensity.

[Reflection chromaticity]
A resin BM having a predetermined film thickness is formed on a non-alkali glass having a thickness of 0.7 mm, and an ultraviolet-visible spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) is used at an incident angle of 5 ° from the glass surface. Absolute reflection measurements were taken. From the obtained spectrum, the chromaticity value (a ^* , b ^* ) at the D65 light source calculated by the CIE L ^* a ^* b ^* color system and the Y at the D65 light source calculated by the CIE XYZ color system ( The reflectance chromaticity was determined based on the following criteria.
A: Reflectance is 4.2 or more and less than 4.7, and a ^* and b ^* are 1.0 or less B: Reflectance is 4.2 or more and less than 4.7, and a ^* and b ^* are more than 1.0 2.0 or less C: Reflectance is 4.2 or more and less than 4.7, and a ^* or b ^* is more than 2.0 D: Reflectance is 4.7 or more and less than 5.2, and a ^* and b ^* are 1.0 or less E: Reflectance is 4.7 or more and less than 5.2, and a ^* and b ^* are more than 1.0 and 2.0 or less F: Reflectance is 4.7 or more and less than 5.2, and a ^* Or b ^* is over 2.0 G: Reflectance is 5.2 or more.

[Surface resistance value]
Using Hiresta UP MCP-HT450 (manufactured by Mitsubishi Chemical Analytech), the surface resistance value (Ω / □) was measured at an applied voltage of 10 V, and the insulation was determined based on the following criteria.
Excellent: More than the measurement limit (10 ¹⁵ Ω / □ or more) and very high insulation Good: 10 ⁸ Ω / □ or more and less than 10 ¹⁵ Ω / □, and sufficient insulation properties: 10 ⁸ Ω / □ And the insulation is insufficient.

[Particle size]
The primary particle diameter of the fine particles was calculated by observing the primary particle diameters of 100 randomly selected fine particles with an electron microscope and determining the average value.

<Production example>
(Synthesis of polyamic acid A-1)
4,4′-diaminophenyl ether (0.30 molar equivalent), paraphenylenediamine (0.65 molar equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 molar equivalent), γ-butyrolactone 850 g And 850 g of N-methyl-2-pyrrolidone were added, 3,3 ′, 4,4′-oxydiphthalcarboxylic dianhydride (0.9975 molar equivalent) was added, and the mixture was reacted at 80 ° C. for 3 hours. . Furthermore, maleic anhydride (0.02 molar equivalent) was added and reacted at 80 ° C. for 1 hour to obtain a polyamic acid A-1 (polymer concentration 20% by mass) solution.

(Synthesis of polyamic acid A-2)
4,4′-diaminophenyl ether (0.95 molar equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 molar equivalent) and 1700 g (100%) of γ-butyrolactone were charged, Anhydride (0.49 molar equivalent) and benzophenonetetracarboxylic dianhydride (0.50 molar equivalent) were added and reacted at 80 ° C. for 3 hours. Further, maleic anhydride (0.02 molar equivalent) was added, and the mixture was further reacted at 80 ° C. for 1 hour to obtain a polyamic acid A-2 (polymer concentration: 20% by mass) solution.

(Synthesis of acrylic polymer (P-1))
In a 1000 cc four-necked flask, 100 g of isopropyl alcohol was charged, kept at 80 ° C. in an oil bath, sealed with nitrogen, and stirred, 30 g of methyl methacrylate, 40 g of styrene, 30 g of methacrylic acid and N.P. A mixed solution of 2 g of N-azobisisobutyronitrile was dropped with a dropping funnel over 30 minutes. Thereafter, the reaction was continued for 4 hours, 1 g of hydroquinone monomethyl ether was added, and the temperature was returned to room temperature to complete the polymerization. As a result, a solution containing methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) was obtained. Further, 100 g of isopropyl alcohol was added to the solution, 40 g of glycidyl methacrylate and 3 g of triethylbenzylammonium chloride were added and reacted for 3 hours while maintaining the temperature at 75 ° C., reprecipitation with purified water, filtration and drying. Weight average molecular weight (measured by gel permeation chromatography using Mw, tetrahydrofuran as a carrier at a temperature of 23 ° C. and converted using a standard polystyrene calibration curve) 40,000, acid value 110 (mg KOH / g ) Acrylic polymer (P-1) powder. Here, when the reaction rate of glycidyl methacrylate was determined from the change in the polymer acid value before and after the reaction, it was 70%, and the addition amount was 0.73 equivalent.

(Preparation of light shielding material dispersion Bk1)
As a thermal plasma method, 4.0 kg of titanium dioxide powder having an average primary particle size of 40 nm is put into a reaction furnace, then ammonia gas is flowed at a furnace linear velocity of 3 cm / sec, and a reaction is performed at a furnace temperature of 750 ° C. for 6 hours. 3.2 kg of titanium oxynitride (particle size: 40 nm, titanium content: 70.6% by mass, nitrogen content: 18.8% by mass, oxygen content: 8.64% by mass) was obtained. This titanium oxynitride (96 g), polyamic acid solution A-1 (120 g), γ-butyrolactone (114 g), N-methyl-2pyrrolidone (538 g) and 3 methyl-3 methoxybutyl acetate (132 g) were charged into a tank, Rotating speed using an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 70% 0.05 mmφ zirconia beads (YTZ balls; manufactured by Nikkato) after stirring for 1 hour with a homomixer (manufactured by Koki Kokai) Dispersion was carried out at 8 m / s for 2 hours to obtain a light shielding material dispersion Bk1 having a solid content concentration of 12% by mass and a pigment / resin (mass ratio) = 80/20.

(Preparation of light shielding material dispersion Bk2)
Titanium nitride particles as a pigment (manufactured by Wako Pure Chemical Industries, Ltd .; particle size: 50 nm, titanium content: 74.3% by mass, nitrogen content: 20.3% by mass, oxygen content: 2.94% by mass) A light shielding material dispersion Bk2 was obtained in the same manner as in the preparation of the light shielding material dispersion Bk1, except that was used.

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

(Preparation of light shielding material dispersion Bk4)
Titanium nitride particles (manufactured by Wako Pure Chemical Industries, Ltd .; particle size: 50 nm, titanium content: 74.3 mass%, nitrogen content: 20.3 mass%, oxygen content: 2.94 mass%) (200 g ), A 45 mass% solution of acrylic polymer (P-1) in 3-methyl-3-methoxybutanol (100 g) and propylene glycol tertiary butyl ether (700 g) were charged into a tank, stirred with a homomixer for 1 hour, and 0.05 mmφ Dispersion was carried out for 2 hours at a rotational speed of 8 m / s using an ultra apex mill equipped with a centrifugal separator filled with 70% zirconia beads. The solid content concentration was 24.5% by mass, and pigment / resin (mass ratio) = 82 / 18 light shielding material dispersions Bk4 were obtained.

(Preparation of white fine particle dispersion WD1)
Silica (“AEROSIL” (registered trademark) OX50; manufactured by Nippon Aerosil Co., Ltd .; particle size: 40 nm, refractive index: 1.45) (96 g), polyamic acid solution A-1 (120 g), γ-butyrolactone ( 114 g), N-methyl-2pyrrolidone (538 g) and 3 methyl-3-methoxybutyl acetate (132 g) were charged in a tank, stirred for 1 hour with a homomixer, and then centrifuged with 70% 0.05 mmφ zirconia beads. Dispersion was carried out for 2 hours at a rotational speed of 8 m / s using an equipped ultra apex mill to obtain a white fine particle dispersion WD1 having a solid content concentration of 12% by mass and a pigment / resin (mass ratio) = 80/20.

(Preparation of white fine particle dispersion WD2)
The white fine particle dispersion was the same as the production of the white fine particle dispersion WD1 except that calcium carbonate (CWS-50; manufactured by Sakai Chemical Industry Co., Ltd .; particle size: 60 nm, refractive index: 1.57) was used as the white fine particles. A liquid WD2 was obtained.

(Preparation of white fine particle dispersion WD3)
The white fine particle dispersion was the same as the production of the white fine particle dispersion WD1, except that barium sulfate (BF-20; manufactured by Sakai Chemical Industry Co., Ltd .; particle size: 30 nm, refractive index: 1.64) was used as the white fine particles. A liquid WD3 was obtained.

(Preparation of white fine particle dispersion WD4)
Except for using aluminum oxide (“AEROXIDE” (registered trademark) Alu C; manufactured by Nippon Aerosil Co., Ltd .; particle size: 13 nm, refractive index: 1.76) as the white fine particles, the same as the preparation of the white fine particle dispersion WD1. As a result, a white fine particle dispersion WD4 was obtained.

(Preparation of white fine particle dispersion WD5)
The white fine particle dispersion was the same as the production of the white fine particle dispersion WD1 except that barium sulfate (BF-40; manufactured by Sakai Chemical Industry Co., Ltd .; particle size: 10 nm, refractive index: 1.64) was used as the white fine particles. A liquid WD5 was obtained.

(Preparation of white fine particle dispersion WD6)
The white fine particle dispersion was the same as the production of the white fine particle dispersion WD1 except that barium sulfate (BF-1L; manufactured by Sakai Chemical Industry Co., Ltd .; particle size: 100 nm, refractive index: 1.64) was used as the white fine particles. A liquid WD6 was obtained.

(Preparation of white fine particle dispersion WD7)
The white fine particle dispersion was the same as the production of the white fine particle dispersion WD1 except that barium sulfate (B-30; manufactured by Sakai Chemical Industry Co., Ltd .; particle size: 300 nm, refractive index: 1.64) was used as the white fine particles. A liquid WD7 was obtained.

(Preparation of fine particle dispersion WD8)
The fine particle dispersion WD8 is the same as the preparation of the white fine particle dispersion WD1 except that acrylic resin fine particles (FS-106; manufactured by Nippon Paint Co., Ltd .; particle size: 100 nm, refractive index: 1.47) are used as the fine particles. Got.

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

(Preparation of white fine particle dispersion WD23)
A white color was produced 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 size: 40 nm, refractive index: 2.71) was used as the white fine particles. A fine particle dispersion WD23 was obtained.

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

  In the light-shielding material dispersion Bk4 (569.9 g), a 50% by weight solution of propylene glycol monomethyl ether acetate of bisphenoxyethanol full orange acrylate (18.7 g) and dipentaerythritol hexaacrylate (DHPA; Nippon Kayaku Co., Ltd.) as a polyfunctional monomer )) Propylene glycol monomethyl ether acetate solution (25.9 g), Irgacure (registered trademark) 369 (12.9 g) as a photopolymerization initiator, Adeka (registered trademark) Optomer N-1919 (3.5 g; Asahi Denka Kogyo Co., Ltd.), N, N′-tetraethyl-4,4′-diaminobenzophenone (1.3 g) and 10% by mass solution of propylene glycol monomethyl ether acetate (3.6 g) of silicone surfactant. 3-methyl-3-methyl A solution dissolved in toxi-butyl acetate (341.5 g) and propylene glycol monomethyl ether acetate (22.7 g) was added, and the total solid content concentration was 18% by mass, and the pigment / resin (mass ratio) was 70/30. A resin composition UL1 was obtained. In addition, resin contains the non-volatile component of the acrylic polymer (P-1) in a dispersion liquid, a polyfunctional monomer, a photoinitiator, and surfactant.

On a non-alkali glass (1737; made by Corning; thickness 0.7 mm) substrate which is a transparent substrate, the black resin composition LL1 was applied by a spin coater so that the film thickness after curing was 0.7 μm, and at 120 ° C. Semi-curing was performed for 20 minutes to obtain a semi-cured film of the light shielding layer (A) having an OD value of 1.2. Next, photosensitive black resin composition UL1 was applied with a spin coater so that the film thickness after curing was 0.7 μm, and prebaked at 90 ° C. for 10 minutes. The coating film was exposed to ultraviolet rays at an exposure amount of 200 mJ / cm ² through a photomask using a mask aligner PEM-6M (manufactured by Union Optical Co., Ltd.).

  Next, development was performed with an alkali developer of a 0.5% by weight aqueous solution of tetramethylammonium hydroxide, followed by washing with pure water, thereby forming a black matrix pattern that could be used for a color filter substrate. The obtained substrate is kept in a hot air oven at 230 ° C. for 30 minutes and cured, whereby 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 are laminated. A black matrix substrate with an OD value of 4.0 was obtained.

(Examples 2 to 7)
Black resin compositions LL2 to LL7 were obtained in the same manner as in Example 1 except that the white fine particle dispersions WD2 to WD7 were used instead of WD1 as the white fine particle dispersions to be used. 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 were laminated in the same manner as in Example 1 except that these black resin compositions LL2 to LL7 were used. A black matrix substrate having an OD value of 4.0 was obtained.

(Example 8)
After mixing the light-shielding material dispersion Bk2 (364 g) and the white fine particle dispersion WD3 (364 g), polyamic acid A-1 (63 g), γ-butyrolactone (82 g), N-methyl-2-pyrrolidone (87 g), 3-methyl-3-methoxybutyl acetate (39 g) and surfactant LC951 (1 g) (manufactured by Enomoto Kasei) were added, and the total solid content concentration was 10% by mass, light shielding material / white fine particles / resin (mass ratio) = 35/35. / 30 black resin composition LL8 was obtained. Except for using this black resin composition LL8, an OD value of 4 was obtained by laminating 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 in the same manner as in Example 1. A black matrix substrate of 2 was obtained.

Example 9
After mixing the light-shielding material dispersion Bk3 (364 g) and the white fine particle dispersion WD5 (364 g), polyamic acid A-1 (63 g), γ-butyrolactone (82 g), N-methyl-2-pyrrolidone (87 g), Black resin with 3 methyl-3 methoxybutyl acetate (39 g) and surfactant LC951 (1 g) added, total solid content concentration 10 mass%, light shielding material / white fine particles / resin (mass ratio) = 35/35/30 Composition LL9 was obtained. Except for using this black resin composition LL9, an OD value of 3 was obtained by laminating 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 in the same manner as in Example 1. 8 black matrix substrate was obtained.

(Example 10)
On a non-alkali glass (1737) substrate, which is a transparent substrate, the resin composition LL3 is applied by a spin coater so that the film thickness after curing is 0.7 μm, and semi-cured at 120 ° C. for 20 minutes, and the OD value is A semi-cured film of 1.2 light shielding layer (A) was obtained. Next, a positive photoresist (SRC-100; manufactured by Shipley Co., Ltd.) was applied with a spin coater, and prebaked at 90 ° C. for 10 minutes. A mask aligner PEM-6M is used for this coating film, UV light is exposed through a positive photomask at an exposure amount of 200 mJ / cm ² , and a positive type using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. After developing the resist and etching the polyimide precursor at the same time, the positive resist was stripped with methyl cellosolve acetate. Subsequently, the film was cured at 230 ° C. for 30 minutes to produce a light shielding layer (A) having a thickness of 0.7 μm and an OD value of 1.2.

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

Next, the non-photosensitive resin composition UL2 was applied onto the substrate on which the light-shielding layer (A) was prepared with a spin coater so that the film thickness after curing was 0.7 μm, and semi-cured at 120 ° C. for 20 minutes. . Subsequently, a positive photoresist (SRC-100) was applied with a spin coater and pre-baked at 90 ° C. for 10 minutes. A mask aligner PEM-6M is used for this coating film, UV light is exposed through a positive photomask at an exposure amount of 200 mJ / cm ² , and a positive type using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. After developing the resist and etching the polyimide precursor at the same time, the positive resist was stripped with methyl cellosolve acetate. Subsequently, curing was performed at 230 ° C. for 30 minutes, and a light shielding layer (A) having a thickness of 0.7 μm and an OD value of 1.2 was laminated with a light shielding layer (B) having a thickness of 0.7 μm and an OD value of 2.8. A resin black matrix substrate was obtained.

(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 to be used. An OD value obtained by laminating 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 in the same manner as in Example 1 except that this black resin composition LL8 was used. A 4.0 black matrix substrate was obtained.

(Comparative Example 1)
To the light-shielding material dispersion Bk1 (728 g), polyamic acid A-1 (63 g), γ-butyrolactone (82 g), N-methyl-2-pyrrolidone (87 g), 3 methyl-3 methoxybutyl acetate (39 g) and surface activity Agent 951 (1 g) is added, and a black resin composition having a total solid content concentration of 10% by mass and a light shielding material / resin (mass ratio) of 70/30 not containing white fine particles having a refractive index of 1.4 to 1.8 LL21 was obtained.

On a non-alkali glass (1737) substrate, which is a transparent substrate, the black resin composition LL21 is applied with a spin coater so that the film thickness after curing is 0.7 μm, and semi-cured at 120 ° C. for 20 minutes to obtain an OD value. A semi-cured film of the light-shielding layer (A) of 2.5 was obtained. Next, photosensitive black resin composition UL1 was applied with a spin coater so that the film thickness after curing was 0.7 μm, and prebaked at 90 ° C. for 10 minutes. A mask aligner PEM-6M was used for this coating film, and ultraviolet rays were exposed through a photomask at an exposure amount of 200 mJ / cm ² .

  Next, development was performed with an alkali developer of a 0.5 mass% aqueous solution of tetramethylammonium hydroxide, followed by washing with pure water to obtain a patterned substrate. The obtained patterning substrate was kept in a hot air oven at 230 ° C. for 30 minutes and cured to laminate 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. A black matrix substrate having an OD value of 5.3 was obtained.

(Comparative Example 2)
After mixing the light-shielding material dispersion Bk1 (364 g) and the white fine particle dispersion WD22 (364 g), polyamic acid A-1 (63 g), γ-butyrolactone (82 g), N-methyl-2-pyrrolidone (87 g), Black resin composition LL22 was prepared by adding 3 methyl-3 methoxybutyl acetate (39 g) and surfactant LC951 (1 g), but the particles agglomerated to significantly increase the viscosity, and application with a spin coater was not possible. It was possible.

(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. Except for using this black resin composition LL23, an OD value of 4 was obtained by laminating 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 in the same manner as in Example 1. 0.0 resin black matrix substrate was obtained.
<Evaluation results>
Tables 1 and 2 show the compositions of the black resin compositions produced in Examples 1 to 11 and Comparative Examples 1 to 3 and the evaluation results of the produced BM substrates.

  From the results of Tables 1 and 2, the BM substrates produced in Examples 1 to 11 are all suitable for suppressing the influence of external light because the reflection chromaticity and reflectance are low, and the OD value and Since the volume resistance value is sufficiently high, it is clear that it is a high-performance black matrix substrate.

(Production of color filter substrate)
A green pigment (PG36; 44 g), a yellow pigment (PY138; 19 g), polyamic acid A-2 (47 g) and γ-butyrolactone (890 g) are charged into a tank, and stirred for 1 hour with a homomixer (manufactured by Tokushu Kika). G pigment preliminary dispersion G1 was obtained. Thereafter, the preliminary dispersion G1 is supplied to Dynomill KDL (manufactured by Shinmaru Enterprises) filled with 85% of 0.40 mmφ zirconia beads (Traceram beads; manufactured by Toray Industries, Inc.), and dispersed for 3 hours at a rotational speed of 11 m / s. And a G pigment dispersion G1 having a solid content concentration of 7% by mass and a pigment / polymer (mass ratio) of 90/10 was obtained. G pigment dispersion G1 was diluted with polyamic acid A-2 and a solvent to obtain a green resin composition.

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

  A blue pigment (PR15: 6; 63 g) was charged instead of the green pigment and the yellow pigment, and a B pigment dispersion B1 having a solid content concentration of 7% by mass and a pigment / polymer (mass ratio) of 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.

  On each of the black matrix substrates prepared in Examples 1 to 11 and Comparative Examples 1 and 3, a red paste was applied after drying so as to have a film thickness of 2.0 μm, and prebaked to obtain a polyimide precursor red color. A colored film was formed. Using a positive photoresist, red pixels were formed by the same means as described above, and heated to 290 ° C. to perform thermosetting. Similarly, a green paste was applied to form a green pixel, which was then heated to 290 ° C. and thermally cured. Similarly, a blue paste was applied to form a blue pixel, and heated to 290 ° C. to perform thermosetting.

(Production of liquid crystal display device)
Each obtained color filter substrate was washed with a neutral detergent, and then an alignment film made of polyimide resin was applied by a printing method and heated at 250 ° C. for 10 minutes using a hot plate. The thickness of the polyimide resin alignment film after heating was 0.07 μm. Thereafter, each color filter substrate was rubbed, a sealant was applied by a dispensing method, and heated at 90 ° C. for 10 minutes using a hot plate. On the other hand, the substrate on which the TFT array was formed on the glass substrate was similarly washed with a neutral detergent, and then an alignment film was applied and heated. After that, a spherical spacer with a diameter of 5.5 μm is sprayed, and each color filter substrate coated with the sealing agent and the TFT substrate are overlapped and heated in an oven at 160 ° C. for 90 minutes to cure the sealing agent. I got a cell. Each cell was allowed to stand for 4 hours at a temperature of 120 ° C. and a pressure of 13.3 Pa. Subsequently, after standing for 0.5 hours in nitrogen, the liquid crystal compound was filled again under vacuum. The liquid crystal compound was filled by placing the cell in a chamber and reducing the pressure to 13.3 Pa at room temperature, then immersing the liquid crystal inlet in liquid crystal and returning to normal pressure using nitrogen. After filling the liquid crystal, the liquid crystal injection port was sealed with an ultraviolet curable resin. Next, a polarizing plate was attached to the outside of the two glass substrates of the cell to complete the cell. Further, the obtained cell was modularized to complete a liquid crystal display device.

  As a result of observing the obtained liquid crystal display device, when the liquid crystal display device including the black matrix substrate obtained in Examples 1 to 9 and Example 11 is low in both reflection chromaticity and reflectance, it is exposed to external light. However, the display characteristics were good. The liquid crystal display device provided with the black matrix substrate obtained in Example 10 was generally good, but it seemed slightly dark because of a shift in the black matrix pattern. On the other hand, in the liquid crystal display device provided with the black matrix substrate obtained in Comparative Example 1 and Comparative Example 3, since the reflection chromaticity and the reflectance are both high, the black display is observed to float when illuminated by external light. The display quality was inferior.

10: Transparent substrate 11: Resin BM (resin black matrix)
21: Light-shielding layer (A)
22: Light-shielding layer (B)
20: Color filter substrate 23: Pixel 24: Pixel 25: Pixel 26: Overcoat film 28: Transparent electrode 29: Organic EL layer 30: Back electrode layer 31: Insulating film 32: Substrate 33: Extraction electrode 40: Organic EL element

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

Claims (10)

In order, it has a transparent substrate, a light shielding layer (A), and a light shielding layer (B),
The optical density per thickness of the light shielding layer (A) is lower than the optical density per thickness of the light shielding layer (B), and the light shielding layer (A) contains a light shielding material and fine particles having a refractive index of 1.4 to 1.8. A black matrix substrate.   The fine particles having a refractive index of 1.4 to 1.8 are at least one selected from the group consisting of aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, and sodium metasilicate. The black matrix substrate according to claim 1, which is a fine particle. 3. The black matrix substrate according to claim 1, wherein fine particles having a refractive index of 1.4 to 1.8 have a whiteness measured by a method according to JIS P8148 (2001) of 30% or more. The black matrix substrate according to claim 1, wherein the transparent substrate is made of a polyimide resin.
  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 colored pixels are present in portions where no pattern exists. , Color filter substrate.   A light emitting device comprising the color filter substrate according to claim 5 and a light emitting element.   The light emitting device according to claim 6, wherein the light emitting element is an organic EL element.   A liquid crystal display device comprising the color filter substrate according to claim 5, a liquid crystal compound, and a counter substrate in order. Above the transparent substrate,
A step of forming a layer of a composition containing a light shielding material and fine particles having a refractive index of 1.4 to 1.8, a step of forming a layer of a photosensitive resin composition containing a light shielding material above the layer,
The method for producing a black matrix substrate according to any one of claims 1 to 4, further comprising a step of performing pattern exposure and patterning the two kinds of layers with a developer or a solvent. A method for manufacturing a color filter, comprising: a step of providing a pixel in a portion where no pattern exists after a black matrix substrate is manufactured by the method according to claim 9.