JP2015001655A - Laminate resin black matrix substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate resin black matrix substrate in which a laminate resin black matrix having a sufficient optical density as well as having a low reflectance, a neutral reflection tone and excellent insulating property is formed.SOLUTION: A laminate black matrix substrate is provided, which comprises a low optical density layer formed on a transparent substrate and a high optical density layer formed on the low optical density layer. The high optical density layer comprises (a) carbon black and/or titanium carbide and (b) titanium nitride and/or titanium oxynitride, in which a content percentage of the (a) carbon black and/or titanium carbide is 30 to 90 mass% with respect to the total amount of (a) and (b).

Description

  The present invention relates to a laminated resin black matrix substrate.

  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, a metal thin film made of a chromium-based material has been the mainstream of the black matrix formed on the color filter substrate, but a resin black matrix made of a resin and a light-shielding material has been developed to reduce cost and environmental pollution. .

  However, a liquid crystal display device provided with a color filter substrate on which a resin black matrix containing a light shielding material such as carbon black is formed is excellent in indoor visibility, but when used outdoors, it is derived from the black matrix. Deterioration of visibility due to external light reflection has been a problem.

  From such a background, various studies have been made to realize a resin black matrix having a high optical density (OD value) and a low reflectance when viewed from the transparent substrate side. There are a method of forming a two-layer structure of a light absorption layer containing metal fine particles and a reflected light absorption layer (Patent Document 1) and a method of reducing the reflectance by forming a resin black matrix with a two-layer structure (Patent Document 2). Proposed.

Japanese Patent No. 4837297 Japanese Patent No. 5209603

  However, the conventional two-layer resin black matrix does not have sufficient reduction in reflectivity and insulation as a laminated resin black matrix, and in the first place, it is known about the technology to adjust the reflection color tone of the resin black matrix. There was no.

  Accordingly, the present invention provides a laminated resin black matrix substrate in which a laminated resin black matrix having a sufficient optical density, a low reflectance, a neutral reflection color tone, and an excellent insulating property is formed. Objective.

  The present invention provides the laminated resin black matrix substrate described in the following (1) to (7).

(1) A low optical density layer formed on a transparent substrate and a high optical density layer formed on the low optical density layer,
The high optical density layer includes (a) carbon black and / or titanium carbide, and (b) titanium nitride and / or titanium oxynitride, and the above (a) with respect to the total amount of (a) and (b). A laminated black matrix substrate, wherein the content ratio of carbon black and / or titanium carbide is 30 to 90% by mass.
(2) The laminated black matrix substrate according to (1), wherein an OD value per 1 μm of film thickness of the low optical density layer is 0.3 to 2.0.
(3) The surface resistance value is 10 ¹⁵ Ω / □ or more, and the total film thickness of the low optical density layer and the high optical density layer is 1.5 μm or less (1) or (2) Black matrix substrate.
(4) The OD value per 1 μm of the film thickness of the high optical density layer is 3.0 or more, and the film thickness of the high optical density layer is 1.0 μm or less of (1) to (3) The laminated black matrix substrate according to any one of claims.
(5) The laminated black matrix substrate according to any one of (1) to (4), wherein the low optical density layer has an OD value of 0.2 or more.
(6) A color filter substrate in which red, green, or blue pixels are formed in the opening of the laminated resin black matrix substrate according to any one of (1) to (5).
(7) A liquid crystal display device in which a liquid crystal compound is filled between the color filter substrate according to (6) and a counter substrate.

  According to the multilayer resin black matrix formed on the multilayer resin black matrix substrate of the present invention, sufficient light shielding ability to prevent the backlight from passing through can be realized with a thin film, and a high-contrast and clear image can be obtained. In addition, since the reflectance is low and the reflection color tone is neutral, it is possible to obtain a liquid crystal display device that is extremely excellent in visibility even under external light and has high electrical reliability.

  A laminated resin black matrix (hereinafter, “laminated resin BM”) substrate of the present invention comprises a low optical density layer formed on a transparent substrate and a high optical density layer formed on the low optical density layer. The high optical density layer contains (a) carbon black and / or titanium carbide, and (b) titanium nitride and / or titanium oxynitride, and the content ratio of (a) carbon black and / or titanium carbide is 30. It is -90 mass%.

  The OD value of a black matrix (hereinafter referred to as “BM”) consisting of two layers of a low optical density layer and a high optical density layer, that is, a two-layer BM is preferably 3.5 or more. If the OD value of the two-layer BM is less than 3.5, the light shielding property is insufficient, which causes light leakage of the backlight.

  The OD value per 1 μm film thickness of the low optical density layer is preferably 0.3 to 2.0. If the OD value per 1 μm thickness of the low optical density layer is less than 0.2, it is necessary to increase the thickness in order to obtain the desired transmission chromaticity and light shielding property, and the visibility as a color filter is high. It can get worse. On the other hand, when the OD value per 1 μm thickness of the low optical density layer exceeds 2.0, it is necessary to increase the concentration of the pigment contained in the laminated resin BM, and the reflectance of the laminated resin BM becomes high. There is a fear. The OD value as the low optical density layer is preferably 0.2 or more. When the OD value of the low optical density layer is smaller than 0.2, the interface is strongly affected by the interface reflection between the low optical density layer and the high optical density layer, so that the low reflectance may not be realized.

  The OD value per 1 μm film thickness of the high optical density layer is preferably 3.0 or more, and more preferably 3.0 to 6.0. If the OD value per 1 μm film thickness of the high optical density layer is less than 3.0, the film thickness must be increased to obtain the desired light-shielding property, and the visibility as a color filter may deteriorate. There is.

  As a method of forming the low optical density layer and the high optical density layer, for example, both the low optical density layer and the high optical density layer are formed by a photolithography method using a photosensitive black resin composition, or non-photosensitive For example, a method of forming a high optical density layer in a lump by a photolithography method after forming a low-density optical density layer. From the viewpoint of workability, at least the high optical density layer is a photosensitive resin composition and is preferably processed by a photolithography method.

  The black resin composition used for the formation of the laminated resin BM (except when there is no particular notice and the context does not clearly indicate that the “black resin composition” is simply referred to as a low optical density layer) Is a description of both the black resin composition to be formed and the black resin composition to form the high optical density layer), which contains a colorant, an alkali-soluble resin, and a solvent, and is a photosensitive resin composition Further contains a photopolymerization initiator. As the colorant contained in the black resin composition used for forming the high optical density layer, that is, the colorant that the high optical density layer contains, carbon black and / or titanium carbide, and titanium nitride and / or It is necessary to contain titanium oxynitride, and when only carbon black or titanium carbide is contained, the insulating property is poor, which may cause malfunction of the liquid crystal display device. On the other hand, when only titanium nitride or titanium oxynitride is included, the reflection color tone is reddish, and the reflection color tone as the two-layer BM cannot be made neutral.

  Examples of the colorant contained in the black resin composition used for forming the low optical density layer, that is, the colorant contained in the low optical density layer include, for example, carbon black, titanium black, chromium oxide, iron oxide, aniline. Black, perylene pigment or C.I. I. Black pigment such as Solvent Black 123, carbon black coated with resin, inorganic black pigment such as composite oxide such as titanium, manganese, iron, copper or cobalt, or a combination of organic pigment and black pigment, and 2 Although the combination of the organic pigment of a seed | species or more is mentioned, it is not specifically limited.

  Examples of the alkali-soluble resin used in the black resin composition in the present invention include an epoxy resin, an acrylic resin, a siloxane polymer resin, or a polyimide resin, and are excellent in the storage stability of the composition and the heat resistance of the coating film. Acrylic resin or polyimide resin is preferred.

  As the acrylic resin, an acrylic resin having a carboxyl group is preferably used. As the acrylic resin having a carboxyl group, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferable. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds.

  Examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylic acid n-pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls An aromatic vinyl compound such as len, o-methylstyrene, m-methylstyrene or α-methylstyrene, an unsaturated carboxylic acid aminoalkyl ester such as aminoethyl acrylate, an unsaturated carboxylic acid glycidyl ester such as glycidyl acrylate or glycidyl methacrylate, Carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene or isoprene, acryloyl groups or Examples include polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate or polybutyl methacrylate, 2-4 quaternary copolymer selected from tacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate or styrene, average molecular weight (Mw) 2,000-100,000, acid value 70-150 (mgKOH / G) is preferred from the viewpoint of solubility in an alkaline developer. If it is out of this range, the dissolution rate with respect to the alkaline developer is lowered or becomes too fast.

  In addition, it is preferable to use an acrylic resin having an ethylenically unsaturated group in the side chain because the sensitivity during exposure and development is improved. As the ethylenically unsaturated group, an acryl group or a methacryl group is preferable. Such an acrylic resin can be obtained by adding an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to a carboxyl group of an acrylic (co) polymer having a carboxyl group.

  As the acrylic resin having an ethylenically unsaturated group in the side chain, for example, an acrylic resin described in known literatures (Japanese Patent No. 3120476 and JP-A-8-262221), or a photocuring which is a commercially available acrylic resin Resin "Cyclomer (registered trademark) P" (Daicel Chemical Industries, Ltd.) or alkali-soluble cardo resin. Above all, an acrylic resin having an ethylenically unsaturated group in the side chain has an average molecular weight (Mw) of 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve) And an acrylic resin having an acid value of 70 to 150 (mg KOH / g) is preferable from the viewpoints of photosensitive characteristics, solubility in an ester solvent, and solubility in an alkali developer.

  A monomer can be further added to the black resin composition used in the present invention. Examples of the monomer include polyfunctional or monofunctional 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 Esters, propylene oxide (phthalate) anhydride (meth) acrylate, trimellitic acid diethylene glycol (meth) acrylate, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, known literature (Japanese Patent No. 3621533 and special Full orange acrylate oligomer described in Kaihei 8-278630), tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, 2,2-bis [4- (3-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 Examples include full orange acrylate or biscresol full orange methacrylate. These can be used alone or in combination.

  By selecting and combining these polyfunctional or monofunctional acrylic monomers or oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, a compound having 3 or more functional groups is preferable, a compound having 5 or more functional groups is more preferable, and dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate is more preferable.

  When using a pigment that absorbs ultraviolet rays that is effective for photocrosslinking, such as black pigment, in addition to dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate, the molecule contains many aromatic rings. It is preferable to use a (meth) acrylate having a fluorene ring having high water repellency, because the pattern can be controlled to a desired shape during development. Among them, a mixture of 10 to 60 parts by weight of dipentaerythritol hexa (meth) acrylate and / or dipentaerythritol penta (meth) acrylate and 90 to 40 parts by weight of (meth) acrylate having a fluorene ring is used as a monomer. Is preferred.

  Examples of the photopolymerization initiator that can be contained when the black resin composition is photosensitive include, for example, benzophenone compounds, acetophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, and benzoxazole compounds. And inorganic photopolymerization initiators such as oxime ester compounds, carbazole compounds, triazine compounds, phosphorus compounds, and titanates.

  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 (manufactured by Ciba Specialty Chemicals), "Irgacure (registered trademark)" 37 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by Ciba Specialty Chemicals), CGI 2-113- [4-methylbenzyl] -2-dimethylamino-1- (4-morpholinophenyl) -butanone (manufactured by Ciba Specialty Chemicals), t-butylanthraquinone, 1-chloroanthraquinone 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole Dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, “Irgacure®” OXE01, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime) )] (Manufactured by Ciba Specialty Chemicals Co., Ltd.), “Irgacure (registered trademark)” Etanone which is OXE02, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime), an ethanone that is CGI-242, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime), 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl) -s-triazine (Ciba Specialty Chemical) ADEKA (registered trademark) optomer "N-1818, N-1919 or" ADEKA (registered trademark) Cruise "NCI-831 (above, manufactured by Asahi Denka Kogyo Co., Ltd.) It is done.

  These photopolymerization initiators can be used in combination of two or more. Among them, "Irgacure (registered trademark)" 379, "Irgacure (registered trademark)" OXE02, "Adeka (registered trademark) Optomer" N-1919 And two types selected from the group consisting of “ADEKA (registered trademark) Cruise” NCI-831 are preferable because a photosensitive black resin composition having high sensitivity and good pattern shape can be obtained.

  Furthermore, an adhesion improving agent can be added for the purpose of improving the adhesion to an inorganic material such as a glass plate or a silicon wafer. As the adhesion improving agent, for example, a silane coupling agent or a titanium coupling agent can be used. The addition amount of the adhesion improving agent is usually about 0.2 to 20% by mass based on the mass of the polyimide resin or acrylic resin.

  In the black resin composition used in the present invention, a polymer dispersant can be added for the purpose of improving the dispersion stability of the light shielding material. Examples of the polymer dispersant include a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, and a polyallylamine polymer dispersant. These polymer dispersants are desirably added to such an extent that the photosensitivity and adhesion are not deteriorated, and the addition amount is usually about 1 to 40% by mass with respect to the light shielding material.

  In the black resin composition of the present invention, the weight composition ratio of the light shielding material / resin component is preferably in the range of 80/20 to 40/60, and preferably in the range of 75/25 to 50/50. Is more preferable in terms of the balance between the properties, pattern processability, and OD value. Here, the resin component is the total of the polymer, monomer, oligomer and polymer dispersant. If the amount of the resin component is too small, the adhesion of the black coating to the substrate becomes poor. Conversely, if the amount of the light shielding material is too small, the optical density per unit thickness (OD value / μm) is lowered, causing a problem.

  As the solvent used in the black resin composition of the present invention, water or an organic solvent can be used in accordance with the dispersion stability of the pigment to be dispersed and the solubility of the resin to be added. Examples of the organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, or lactone polar solvents. preferable. Mixing with other organic solvents is also preferred.

  Since it is preferable to use an acrylic resin or a polyimide resin as the alkali-soluble resin, the organic solvent is preferably an organic solvent that dissolves the acrylic resin or the polyimide resin. More specifically, for example, when an acrylic resin is used, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, propylene glycol monoethyl ether acetate, diethyl oxalate, aceto Ethyl acetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentylpropionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Examples include ether acetate, pentyl acetate, or propylene glycol monomethyl ether acetate.

  Examples of the solvent other than the above include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, monoethyl ether, methyl carbitol, ethyl carbitol, propylene glycol monomethyl ether, propylene (Poly) alkylene glycol ether solvents such as glycol monoethyl ether, propylene glycol tertiary butyl ether (boiling point 153 ° C.) or dipropylene glycol monomethyl ether, aliphatic esters such as ethyl acetate, butyl acetate or isopentyl acetate, butanol, 3 -Aliphatic alcohols such as methyl-2-butanol or 3-methyl-3-methoxybutanol; Ketones such as Ropentanon or cyclohexanone, xylene, ethylbenzene or solvent naphtha.

  When polyimide resin is used, for example, esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, N-methyl-2-pyrrolidone, N, N-dimethylacetamide or N, N- Examples include amide polar solvents such as dimethylformamide or lactones, 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 weight ratio of lactones in the total solvent. The lactone refers to an aliphatic cyclic ester compound having 3 to 12 carbon atoms. Examples of lactones include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. From the viewpoint of solubility of the polyimide precursor, γ- Butyrolactone is preferred. Examples of solvents other than lactones include 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol mono-methyl ether, propylene glycol mono-methyl ether acetate, Dipropylene glycol-mono-methyl ether, tripropylene glycol-mono-methyl ether, propylene glycol-mono-tertiary-butyl ether, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, Examples include methyl carbitol acetate, ethyl carbitol or ethyl carbitol acetate.

  Since application by a die coating apparatus has become mainstream as the size of the substrate increases, a mixed solvent of two or more components is preferable in order to achieve appropriate volatility and drying properties.

  In addition, a surfactant may be added to the black resin composition of the present invention for the purpose of preventing Benard cells while improving the coatability and the smoothness of the colored coating. The addition amount of the surfactant is preferably 0.001 to 10% by mass of the pigment, and more preferably 0.01 to 1% by mass. If the addition amount is too small, the coating property and the smoothness of the colored coating are not improved and the effect of preventing Benard cell is not obtained. If the addition amount is too large, the physical properties of the coating film may be poor. 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. In the present invention, one or more of these surfactants can be used.

  In the black resin composition of the present invention, the solid content concentration of the resin component (including additives such as monomers and oligomers and a photopolymerization initiator) and the light shielding material is 2 to 2 from the viewpoint of coating properties and drying properties. 30 mass% is preferable and 5-20 mass% is more preferable. Accordingly, the photosensitive black resin composition of the present invention preferably consists essentially of a solvent, a resin component and a light shielding material, and more preferably the total amount of the resin component and the light shielding material is 2 to 30% by mass. 5 to 20% by mass is more preferable. The remainder excluding the solid content is a solvent, and as described above, may further contain a surfactant.

  Examples of the method for producing the photosensitive black resin composition in the present invention include a method of directly dispersing a pigment in a resin solution using a disperser, or a method of dispersing a pigment in water or an organic solvent using a disperser. Then, a method of preparing a pigment dispersion and then mixing it with a resin solution can be mentioned. Examples of the method for dispersing the pigment include a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill. 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. Examples of beads of the bead mill include titania beads, zirconia beads, and zircon beads. 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 size of the pigment and the secondary particle size formed by aggregation of the primary particles are small, it is preferable to use fine dispersed beads of 0.03 to 0.10 mm. 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 dispersing a pigment containing coarse particles of about submicron, it is preferable to use a dispersion bead of 0.10 mm or more because sufficient pulverization force can be obtained and the pigment can be finely dispersed.

  A production example of the laminated resin BM substrate of the present invention is shown below. Examples of the method for applying the photosensitive black resin composition on the transparent substrate include a dipping method, a roll coater method, a spinner method, a die coating method, a method using a wire bar, and a transparent substrate in a solution of the photosensitive black resin composition. And a method of spraying a solution of the photosensitive black resin composition on a transparent substrate. Examples of the transparent substrate include quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as soda lime glass whose surface is silica-coated, or an organic plastic film or sheet. In addition, when apply | coating on a board | substrate, if the board | substrate surface is processed with adhesion assistants, such as a silane coupling agent, an aluminum chelating agent, or a titanium chelating agent, the adhesive force of BM film and a board | substrate can be improved. .

  After apply | coating a black resin fat composition on a transparent substrate, heat drying and hardening are performed by air drying, heat drying, vacuum drying, etc., and a dry film is formed. In order to suppress drying unevenness or transport unevenness when forming the coating, it is preferable to dry and cure the transparent substrate coated with the coating liquid after being dried under reduced pressure using a vacuum dryer equipped with a heating device.

  The dry film thus obtained is usually patterned using a method such as photolithography. The dry film obtained from the photosensitive resin can be exposed or developed as it is or after an oxygen-blocking film is formed on the surface thereof to form a desired pattern. Thereafter, the oxygen blocking film is removed as necessary, and then heat-cured to obtain a laminated resin BM substrate. The heat curing conditions vary depending on the resin, but when an acrylic resin is used, it is usually 1 to 60 minutes at 200 to 250 ° C, and when a polyimide resin is used, it is usually 1 to 60 minutes at 250 to 300 ° C. It is common to heat.

  A color filter substrate for liquid crystal display can be produced using the laminated resin BM substrate of the present invention. That is, the present invention can provide a color filter substrate for liquid crystal display comprising the laminated resin BM substrate of the present invention. The color filter includes at least a layered resin BM substrate in which a layered resin BM is formed on a partial region of the transparent substrate, and a pixel formed in a region on the transparent substrate where the layered resin BM is not formed. It is a filter, The said laminated resin BM board | substrate is a laminated resin BM board | substrate of this invention.

  In addition, the reflection chromaticity of the laminated resin BM is measured from the surface on the substrate side, and calculated by the CIE L * a * b * color system using the reflection spectrum for the standard C light source according to the method of JIS-Z8729. It is common to use the determined chromaticity values (a *, b *). However, since the laminated resin BM in the laminated resin BM substrate of the present invention is composed of multiple layers, the light reflected at the interface of each layer interferes, and the measured value may not match the visually recognized hue. Therefore, in the present invention, a sample BM formed with printing ink was used as a comparison object, and a judgment was made by visual sensory evaluation under sunlight. As the reflection color tone, it is preferable that the reflection color tone is less glossy and bluish, that is, a neutral reflection color tone.

  In the above description, each component can be used alone or in combination of two or more, unless it is clear from the context.

  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>
[OD value]
A resin BM having a film thickness of 1.0 μm 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 an X-rite 361T (visual) densitometer. Calculated from 1).
OD value = log ₁₀ (I ₀ / I) (1)
I ₀ : Incident light intensity I: Transmitted light intensity

[Film thickness]
The film thickness of the laminated resin BM is measured twice using a stylus-type surface step meter DEKTAKFPD-500 manufactured by Nippon Vacuum Co., Ltd., by scratching an arbitrary portion of the formed laminated resin BM and exposing the glass surface. The average value was measured.

[Reflection chromaticity]
A laminated resin BM having a desired film thickness was formed on an alkali-free glass having a thickness of 0.7 mm, and the reflection chromaticity from the glass surface was measured using a spectrophotometer (UV-2500PC; manufactured by Shimadzu Corporation) ( Measurement wavelength region: 300 to 780 nm, sampling pitch: 1.0 nm, scan speed: low speed, slit width: 2.0 nm).

[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 1000 V, and the insulation was determined based on the following criteria.

[Reflection color tone]
Black printing ink (GLS-912; manufactured by Teikoku Ink) was printed on a non-alkali glass with a thickness of 0.7 mm using a 230 mesh plate so that the thickness after drying was 10 μm, and then oven-dried at 150 ° C. for 30 minutes. A sample BM was prepared.

A desired laminated resin BM was formed on a non-alkali glass having a thickness of 0.7 mm, and visually compared with a sample BM under sunlight, and the reflection color tone was determined based on the following criteria.
○: Very good visibility (black with deep black)
Δ: Good visibility (black with neutral color)
×: Visibility is poor (reddish black)

<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 acrylic polymer (P-1))
After synthesizing a methyl methacrylate / methacrylic acid / styrene copolymer (weight ratio 30/40/30) by the method described in the literature (Patent No. 3120476; Example 1), 40 parts by weight of glycidyl methacrylate was added and purified. By reprecipitation with water, filtration and drying, an acrylic polymer (P-1) powder having an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH / g) was obtained.

(Preparation of titanium nitride dispersion (Bk-1))
Titanium nitride particles produced by thermal plasma method (Nisshin Engineering Co., Ltd .: 96 g), polyamic acid solution A-1 (120 g), γ-butyrolactone (114 g), N-methyl-2pyrrolidone (538 g) and 3 A centrifuge separator charged with 70% of 0.05 mmφ zirconia beads (YTZ balls; manufactured by Nikkato) was charged in a tank with methyl-3 methoxybutyl acetate (132 g), stirred for 1 hour with a homomixer (made by Special Machine) Using an ultra apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) for 2 hours at a rotational speed of 8 m / s, a light shielding material dispersion Bk-1 having a solid content concentration of 12% by mass and a pigment / resin (weight ratio) = 80/20 Got.

(Preparation of carbon black dispersion (Bk-2))
Carbon black (TPX1291; manufactured by CABOT; 400 g), propylene glycol monomethyl ether acetate 40 mass% solution (187.5 g) of acrylic resin (P-1), polymer dispersant (BYK21116; manufactured by BYK Chemie; 62.5 g) And propylene glycol monoethyl ether acetate (890 g) were charged into a tank and stirred for 1 hour with a homomixer (manufactured by Tokushu Kika) to obtain Preliminary Dispersion 2. Thereafter, the preliminary dispersion 2 was supplied to an ultra apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 70% of 0.10 mmφ zirconia beads (manufactured by Toray Industries), and dispersed for 2 hours at a rotational speed of 8 m / s. The carbon black pigment dispersion liquid Bk-2 having a solid content concentration of 25% by mass and a pigment / resin (weight ratio) = 80/20 was obtained.

(Preparation of titanium carbide dispersion (Bk-3))
Carbonization was performed in the same manner as in the preparation of the light-shielding material dispersion Bk-2, except that titanium carbide particles (manufactured by Nissin Engineering Co., Ltd., TiC nano powder Lot: 1330709111; 400 g) manufactured by a thermal plasma method were used as pigments A titanium dispersion Bk-3 was obtained.

(Preparation of titanium nitride dispersion (Bk-4))
A titanium nitride dispersion Bk-4 was obtained in the same manner as the preparation of the light-shielding material dispersion Bk-2 except that titanium nitride particles (Nisshin Engineering Co., Ltd .; 400 g) produced by the thermal plasma method were used. .

(Preparation of titanium oxynitride dispersion (Bk-5))
Titanium oxynitride (particle size: 40 nm, titanium content: 70.6 mass%, nitrogen content: 18.8 mass%) described in the literature (JP 2010-95716 A; sample 8 in paragraph 119) as a pigment A titanium oxynitride dispersion Bk-5 was obtained in the same manner as in the preparation of the light shielding material dispersion Bk-2, except that the oxygen content was 8.64% by mass; 400 g).

Example 1
The light-shielding material dispersion Bk-1 (12.50 g), polyamic acid A-1 (42.30 g), γ-butyrolactone (28.21 g), N-methyl-2-pyrrolidone (16.59 g), and surface activity Agent LC951 (0.40 g) was added to obtain a black resin composition PB-1 having a total solid content concentration of 10 mass% and a light shielding material / resin (weight ratio) = 12/88.

  In addition, “ADEKA (registered trademark) NCI-831 (0.48 g) as a photopolymerization initiator was added to propylene glycol monoethyl ether acetate (19.51 g) and stirred until the solid content was dissolved.

  Furthermore, propylene glycol monomethyl ether acetate 40% by mass solution (4.65 g) of acrylic polymer (P-1), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, propylene glycol monoethyl ether acetate A 50% by mass solution (3.43 g) and a 10% by mass propylene glycol monoethyl ether acetate solution (0.24 g) of a silicone surfactant BYK333 as a surfactant were added and stirred at room temperature for 1 hour. A photosensitive resist was obtained. By adding 15.85 g of the pigment dispersion BK-2 and 15.85 g of the pigment dispersion BK-4 to this photosensitive resist, the total solid content concentration is 20% by mass, and the pigment / resin (weight ratio) = 55/45. A photosensitive black resin composition AB-1 was prepared.

On a non-alkali glass (1737; made by Corning; thickness 0.7 mm) substrate which is a transparent substrate, the black resin composition PB-1 was applied with a spin coater so that the film thickness after curing was 0.7 μm. Semi-curing was carried out at 20 ° C. for 20 minutes to obtain a semi-cured film having a low optical density layer having an OD value of 0.7. Next, photosensitive black resin composition AB-1 was applied by a spin coater so that the film thickness after curing was 0.8 μm, and prebaked at 90 ° C. for 10 minutes. A mask aligner PEM-6M (manufactured by Union Optics Co., Ltd.) was used for this coating film, and ultraviolet rays were exposed at a dose of 200 mJ / cm ² through a photomask.

  Next, it developed with the 0.5 mass% aqueous solution of an aqueous solution of tetramethylammonium hydroxide, and then washed 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, whereby a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.6 were laminated. A laminated resin BM substrate 1 having a value of 4.3 was obtained.

(Example 2)
The ratio of the dispersion constituting the photosensitive resin composition used for the high optical density layer was Bk-2 / Bk-4 = 70/30 (22.19 g of the above pigment dispersion BK-2 in the photosensitive resist, pigment dispersion) A photosensitive resin composition AB-2 was obtained in the same manner as in Example 1 except that 9.51 g of liquid BK-4 was added. In the same manner as in Example 1 using PB-1 and AB-2, a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.4 were laminated, and an OD value of 4.1. A laminated resin BM substrate 2 was obtained.

Example 3
The ratio of the dispersion constituting the photosensitive resin composition used for the high optical density layer was Bk-2 / Bk-4 = 90/10 (28.53 g of the above pigment dispersion BK-2 in the photosensitive resist, pigment dispersion A photosensitive resin composition AB-3 was obtained in the same manner as in Example 1 except that 3.17 g of liquid BK-4 was added. In the same manner as in Example 1 using PB-1 and AB-3, an OD value of 4.0, in which a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.3 were laminated. A laminated resin BM substrate 3 was obtained.

Example 4
The ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was Bk-2 / Bk-4 = 30/70 (9.51 g of the pigment dispersion BK-2 in the photosensitive resist, pigment dispersion) A photosensitive resin composition AB-4 was obtained in the same manner as in Example 1 except that 22.19 g of the liquid BK-4 was added. In the same manner as in Example 1 using PB-1 and AB-4, an OD value of 4.4, in which a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.7 were laminated. A laminated resin BM substrate 4 was obtained.

(Example 5)
The ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was Bk-3 / Bk-4 = 50/50 (15.85 g of the above pigment dispersion BK-3 in the photosensitive resist, pigment dispersion A photosensitive resin composition AB-5 was obtained in the same manner as in Example 1 except that 15.85 g of liquid BK-4 was added. In the same manner as in Example 1 using PB-1 and AB-5, an OD value of 4.6, in which a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.9 were laminated. A laminated resin BM substrate 5 was obtained.

(Example 6)
The ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was Bk-3 / Bk-4 = 90/10 (28.53 g of the above pigment dispersion BK-3 in the photosensitive resist, pigment dispersion A photosensitive resin composition AB-6 was obtained in the same manner as in Example 1 except that 3.17 g of liquid BK-4 was added. In the same manner as in Example 1 using PB-1 and AB-6, a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.8 were laminated. A laminated resin BM substrate 6 was obtained.

(Example 7)
The ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was Bk-3 / Bk-4 = 30/70 (9.51 g of the pigment dispersion BK-3 in the photosensitive resist, pigment dispersion) A photosensitive resin composition AB-7 was obtained in the same manner as in Example 1 except that 22.19 g of the liquid BK-4 was added. In the same manner as in Example 1 using PB-1 and AB-7, an OD value of 4.6 was obtained by laminating a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.9. A laminated resin BM substrate 7 was obtained.

(Example 8)
The ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer is Bk-3 / Bk-5 = 50/50 (15.85 g of the above pigment dispersion BK-3 in the photosensitive resist, the pigment dispersion A photosensitive resin composition AB-8 was obtained in the same manner as in Example 1 except that 15.85 g of the liquid BK-5 was added. In the same manner as in Example 1 using PB-1 and AB-8, a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.6 were laminated, and an OD value of 4.3. A laminated resin BM substrate 8 was obtained.

Example 9
Photosensitive resin composition AB-9 in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was Bk-2 / Bk-5 = 50/50. Got. In the same manner as in Example 1 using PB-1 and AB-9, an OD value of 4.0, in which a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.3 were laminated. A laminated resin BM substrate 9 was obtained.

(Example 10)
The black resin composition was the same as in Example 1 except that the composition ratio of the black resin composition used for the low optical density layer was 10% by mass of the total solid content and the light shielding material / resin (weight ratio) = 5/95. PB-2 was obtained. In the same manner as in Example 1 using PB-2 and AB-1, an OD value of 3.8 was obtained by laminating a low optical density layer having an OD value of 0.2 and a high optical density layer having an OD value of 3.6. A laminated resin BM substrate 10 was obtained.

(Example 11)
The black resin composition was the same as in Example 1 except that the composition ratio of the black resin composition used for the low optical density layer was 10% by mass of the total solid content and the light shielding material / resin (weight ratio) = 25/75. PB-3 was obtained. In the same manner as in Example 1 using PB-3 and AB-1, an OD value of 5.0 was obtained by laminating a low optical density layer having an OD value of 1.4 and a high optical density layer having an OD value of 3.6. A laminated resin BM substrate 11 was obtained.

(Example 12)
The black resin composition was the same as in Example 1 except that the composition ratio of the black resin composition used for the low optical density layer was 10% by mass of the total solid content and the light shielding material / resin (weight ratio) = 3/97. PB-4 was obtained. In the same manner as in Example 1 using PB-4 and AB-1, an OD value of 3.7 was obtained by laminating a low optical density layer having an OD value of 0.1 and a high optical density layer having an OD value of 3.6. A laminated resin BM substrate 12 was obtained.

(Example 13)
A low optical density layer having an OD value of 0.3 and an OD value of 3.6 were obtained in the same manner as in Example 12 except that the thickness of the black resin composition PB-4 used for the low optical density layer was 1.5 μm. A laminated resin BM substrate 13 having an OD value of 3.9, laminated with a high optical density layer, was obtained.

(Example 14)
The black resin composition was the same as in Example 1 except that the composition ratio of the black resin composition used for the low optical density layer was 10% by mass of the total solid content and the light shielding material / resin (weight ratio) = 30/70. PB-5 was obtained. In the same manner as in Example 1 using PB-5 and AB-1, an OD value of 5.3 was formed by laminating a low optical density layer having an OD value of 1.7 and a high optical density layer having an OD value of 3.6. A laminated resin BM substrate 14 was obtained.

(Comparative Example 1)
Photosensitive resin composition AB-10 in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was Bk-2 / Bk-4 = 10/90. Got. In the same manner as in Example 1 using PB-1 and AB-10, an OD value of 4.6 was obtained by laminating a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.9. A laminated resin BM substrate 15 was obtained.

(Comparative Example 2)
A photosensitive resin composition AB-11 was obtained in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was set to Bk-2 = 100. In the same manner as in Example 1 using PB-1 and AB-11, an OD value of 3.8 in which a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.1 were laminated. A laminated resin BM substrate 16 was obtained.

(Comparative Example 3)
A photosensitive resin composition AB-12 was obtained in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used for the high optical density layer was set to Bk-3 = 100. In the same manner as in Example 1 using PB-1 and AB-12, an OD value of 4.6, in which a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.8 were laminated. A laminated resin BM substrate 17 was obtained.

(Comparative Example 4)
A photosensitive resin composition AB-13 was obtained in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used for the high optical density layer was set to Bk-4 = 100. In the same manner as in Example 1 using PB-1 and AB-13, an OD value of 4.7 in which a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 4.0 were laminated. A laminated resin BM substrate 18 was obtained.

(Comparative Example 5)
A photosensitive resin composition AB-14 was obtained in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was set to Bk-5 = 100. In the same manner as in Example 1 using PB-1 and AB-14, a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.5 were laminated, and an OD value of 4.2. A laminated resin BM substrate 19 was obtained.

(Comparative Example 6)
Photosensitive resin composition AB-15 in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used in the high optical density layer was Bk-4 / Bk-5 = 50/50. Got. In the same manner as in Example 1 using PB-1 and AB-15, an OD value of 4.4 was obtained by laminating a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.7. A laminated resin BM substrate 20 was obtained.

(Comparative Example 7)
Photosensitive resin composition AB-16 in the same manner as in Example 1 except that the ratio of the dispersion constituting the photosensitive resin composition used for the high optical density layer was Bk-2 / Bk-3 = 50/50. Got. In the same manner as in Example 1 using PB-1 and AB-16, a low optical density layer having an OD value of 0.7 and a high optical density layer having an OD value of 3.5 were laminated, and an OD value of 4.2. A laminated resin BM substrate 21 was obtained.

<Evaluation results>
Table 1 shows the compositions of the black resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 7 and the evaluation results of the prepared laminated resin BM substrates.

  From the results of Table 1, in Examples 1 to 12, it is possible to obtain a laminated resin BM that has a neutral reflection color tone and high insulation properties.

  On the other hand, as in Comparative Examples 1 to 7, when the addition ratio of CB / TiC is small in the high optical density layer, or a system using a single pigment, or a pigment mixture system such as TiN / TiON or CB / TiC. The reflection color tone and insulation were deteriorated, and it was impossible to obtain a laminated resin BM having a reflection color tone of neutral and high insulation.

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

Claims (7)

A low optical density layer formed on a transparent substrate, and a high optical density layer formed on the low optical density layer,
The high optical density layer includes (a) carbon black and / or titanium carbide, and (b) titanium nitride and / or titanium oxynitride, and (a) with respect to the total amount of (a) and (b). A laminated black matrix substrate, wherein the content ratio of carbon black and / or titanium carbide is 30 to 90% by mass.   The laminated black matrix substrate according to claim 1, wherein an OD value per 1 μm of the low optical density layer is 0.3 to 2.0. The black matrix substrate according to claim 1 or 2, wherein a surface resistance value is 10 ¹⁵ Ω / □ or more, and a total film thickness of the low optical density layer and the high optical density layer is 1.5 µm or less.   The OD value per 1 μm thickness of the high optical density layer is 3.0 or more, and the thickness of the high optical density layer is 1.0 μm or less. Laminated black matrix substrate.   The laminated black matrix substrate according to any one of claims 1 to 4, wherein an OD value of the low optical density layer is 0.2 or more.   A color filter substrate in which red, green, or blue pixels are formed in the opening of the laminated resin black matrix substrate according to claim 1.   A liquid crystal display device, wherein a liquid crystal compound is filled between the color filter substrate according to claim 6 and the counter substrate.