Resist composition for black matrix and black matrix

Abstract

The present invention provides a black matrix resist composition, which can form a black matrix whose surface resistance value does not decrease even after being subjected to high temperature and long-term post-baking. The black matrix resist composition comprises a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent, and an oxazine compound, wherein the oxazine compound is a compound represented by the following general formula (1) and / or (2). In the general formula (1), R 1 and R 2 represents an alkyl group or an aryl group optionally containing an unsaturated bond, which are optionally the same as or different from each other; X 1 represents any one of the linking groups shown in the following formulae (3) to (5). 3 and R 4 represents an alkyl group or an aryl group optionally containing an unsaturated bond, which are optionally the same as or different from each other; X 2 It is a divalent linking group.

Description

Technical Field

[0001] The present invention relates to a resist composition for a black matrix and a black matrix. Background Art

[0002] In image display devices using liquid crystal, plasma, etc., a light-shielding film (black matrix, also known as "black matrix") is provided in the gaps between the colored patterns in the screen display area and the edges of the surrounding parts of the display area, and also on the external light side of the TFT in a liquid crystal display using TFT.

[0003] Furthermore, in liquid crystal display devices, it is mainly used to prevent leakage from backlight from entering the screen. In plasma display devices, it is mainly used to prevent bleeding caused by the confusion of different colored lights from entering the screen, thereby helping to improve display characteristics (contrast and color purity).

[0004] For example, color filters for converting white light from the backlight source of a liquid crystal display device into colored light are usually manufactured by forming pixels of different hues of red, green, and blue in a striped or mosaic pattern on the surface of a transparent substrate such as glass or plastic sheet formed with a black matrix.

[0005] Furthermore, even in touch panels that align an image display device with a position input device, a color filter formed with a black matrix as a light-shielding film is utilized. Previously, this was typically formed on the side opposite the sensor substrate, separated by a protective glass sheet. However, with the growing demand for lighter touch panels, technology is being developed to achieve even greater weight reduction by simultaneously forming a light-shielding film and a touch sensor on the same side of a protective glass sheet.

[0006] For example, Patent Document 1 discloses a technique in which a specific pigment and carbon black are used in combination as colorants in a photosensitive coloring composition for forming color spacers, and the content ratio of the carbon black is set within a specific range, thereby imparting shielding properties and the like.

[0007] In recent years, image display devices have tended to be used in various scenarios such as mobile use.

[0008] As the use of such image display devices expands, a stronger black matrix is ​​required.

[0009] As a method for strengthening the black matrix, a method of applying a high-temperature and long-term post-bake is sometimes used.

[0010] However, conventional resist compositions for black matrices have a problem in that their surface resistance decreases when they are subjected to high-temperature and long-term post-baking, and there is still room for improvement.

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: Japanese Patent Application Laid-Open No. 2016-177190 Summary of the Invention

[0014] Problems to be solved by the invention

[0015] Therefore, an object of the present invention is to provide a resist composition for a black matrix, which can form a black matrix whose surface resistance does not decrease even after post-baking at a high temperature and for a long time.

[0016] Means used to solve problems

[0017] The present inventors have discovered that by using a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent, and an oxazine compound, and using a compound having a specific structure as the oxazine compound, a black matrix resist composition can be obtained that can form a black matrix whose surface resistance does not decrease even after high-temperature and long-term post-baking, thereby completing the present invention.

[0018] Specifically, the present invention provides a resist composition for a black matrix comprising a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent, and an oxazine compound, wherein the oxazine compound is a compound represented by the following general formula (1) and / or (2).

[0019]

[0020] In the general formula (1), R 1 and R 2 represents an alkyl group or an aryl group optionally containing an unsaturated bond, and is optionally the same as or different from each other. 1 represents any one of the linking groups represented by the following formulae (3) to (5).

[0021] In the general formula (2), R 3 and R 4 represents an alkyl group or an aryl group optionally containing an unsaturated bond, and is optionally the same as or different from each other. 2 It is a divalent linking group.

[0022]

[0023] -O-(5)

[0024] In the resist composition for a black matrix of the present invention, the content of the oxazine compound is preferably 0.1% by mass to 15% by mass in terms of mass fraction relative to the total solid content.

[0025] The present invention also provides a black matrix formed using the resist composition for a black matrix of the present invention.

[0026] Hereinafter, the resist composition for black matrices of the present invention and the black matrix formed therefrom will be described in detail.

[0027] <Resist composition for black matrix>

[0028] The resist composition for a black matrix of the present invention comprises a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent, and an oxazine compound. The oxazine compound is a compound represented by the general formula (1) and / or (2).

[0029] (black colorant)

[0030] The resist composition for a black matrix of the present invention contains a black colorant.

[0031] The black colorant is carbon black having an average primary particle size of 20 to 60 nm, and among them, neutral carbon black having an average primary particle size of 20 to 60 nm and / or acidic carbon black having an average primary particle size of 20 to 60 nm are preferred.

[0032] When the primary particle size of the black colorant is less than 20 nm or greater than 60 nm, the black colorant may not have sufficient light-shielding properties and may also have poor storage stability.

[0033] In addition, the said average primary particle size is the value of the arithmetic mean particle size based on electron microscope observation.

[0034] When the neutral carbon black and the acidic carbon black are used in combination, the mixing ratio (mass ratio) of the neutral carbon black to the acidic carbon black is preferably 85 / 15 to 15 / 85, and more preferably 75 / 25 to 40 / 60.

[0035] When the ratio of neutral carbon black in the above-mentioned carbon black is higher than 85 / 15, the sealing strength may be reduced. When the ratio of acidic carbon black is lower than 15 / 85, the development margin (development latitude) and fine line adhesion (adhesion) may be reduced.

[0036] The above-mentioned acidic carbon black and neutral carbon black will be described.

[0037] Carbon black can be divided into acidic carbon and neutral carbon based on its surface structure. Acidic carbon is a carbonaceous material, either native or artificially acidified, that exhibits acidity when mixed with distilled water and boiled. On the other hand, neutral carbon is known to exhibit a pH at or above neutral when mixed with distilled water and boiled.

[0038] As the above-mentioned neutral carbon black, the pH is preferably in the range of 8.0 to 10.0. Specifically, the examples include: Printex25 (average primary particle size 56 nm, pH 9.5), Printex35 (average primary particle size 31 nm, pH 9.5), Printex65 (average primary particle size 21 nm, pH 9.5) manufactured by Orion Engineered Carbons Co., Ltd., MA#20 (average primary particle size 40 nm, pH 8.0), MA#40 (average primary particle size 40 nm, pH 8.0), MA#30 (average primary particle size 30 nm, pH 8.0) manufactured by Mitsubishi Chemical Corporation, etc.

[0039] As the above-mentioned acidic carbon black, the pH is preferably in the range of 2.0 to 4.0. Specifically, there can be mentioned: Raven 1080 (average primary particle size 28 nm, pH 2.4), Raven 1100 (average primary particle size 32 nm, pH 2.9) manufactured by COLUMBIACHEMICAL, MA-8 (average primary particle size 24 nm, pH 3.0), MA-100 (average primary particle size 22 nm, pH 3.5) manufactured by Mitsubishi Chemical Corporation, SPECIAL BLACK 250 (average primary particle size 56 nm, pH 3.0), SPECIAL BLACK 350 (average primary particle size 31 nm, pH 3.0), SPECIAL BLACK 550 (average primary particle size 25 nm, pH 4.0) manufactured by Orion Engineered Carbons, etc.

[0040] As the black colorant, SPECIALBLACK 250 is preferred from the viewpoints of pigment dispersibility and ensuring resistance value.

[0041] In addition, 1 g of carbon black was added to 20 ml of distilled water (pH 7.0) from which carbon dioxide had been removed and mixed with a magnetic stirrer to prepare an aqueous suspension. The pH (German Industrial Product Standard DIN ISO 787 / 9) was measured at 25°C using a glass electrode.

[0042] The content of the black colorant is preferably 3 to 70% by mass, more preferably 10 to 50% by mass, relative to the total solid content of the resist composition for a black matrix of the present invention.

[0043] When the content of the black colorant is less than 3% by mass, the light-shielding property of a black matrix formed may be reduced. When the content exceeds 70% by mass, it may be difficult to disperse the pigment.

[0044] (Alkali-soluble resin having a carboxyl group)

[0045] The resist composition for black matrices of the present invention contains an alkali-soluble resin having a carboxyl group.

[0046] The alkali-soluble resin having a carboxyl group preferably functions as a binder for the black colorant and is soluble in a developer, particularly an alkaline developer, used in a development step during production of a black matrix.

[0047] The alkali-soluble resin having a carboxyl group may be a block copolymer. By using a block copolymer, the pigment dispersibility can be improved compared to other copolymers, and solubility in PGMEA and alkaline developer can be imparted.

[0048] Among the block copolymers, block copolymers of a block composed of an ethylenically unsaturated monomer having one or more carboxyl groups and a block composed of another copolymerizable ethylenically unsaturated monomer are preferred.

[0049] The block copolymer is not particularly limited, and conventionally used block copolymers can be used. Specifically, examples include copolymers of an ethylenically unsaturated monomer having a carboxyl group, such as acrylic acid or methacrylic acid, and at least one ethylenically unsaturated monomer selected from the group consisting of monomers and oligomers copolymerizable with the ethylenically unsaturated monomer having a carboxyl group, such as styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomers, polymethyl methacrylate macromonomers, and carboepoxy diacrylate.

[0050] However, it is preferred not to use: N-vinylpyrrolidone, monomers containing sulfur elements.

[0051] As the block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used.

[0052] A part of the block portion of the block copolymer may be composed of a random copolymer.

[0053] As the alkali-soluble resin having a carboxyl group, an alkali-soluble Cardo resin may be used.

[0054] Examples of the alkali-soluble cardo resin include epoxy (meth)acrylate acid adducts having a fluorene skeleton, which are addition products of a fluorene epoxy (meth)acrylate derivative and dicarboxylic anhydride and / or tetracarboxylic dianhydride.

[0055] Furthermore, the alkali-soluble resin may have a photopolymerizable functional group.

[0056] The acid value of the alkali-soluble resin having a carboxyl group is preferably 5 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g, further preferably 50 to 150 mgKOH / g, and particularly preferably 70 to 120 mgKOH / g, from the viewpoint of development properties.

[0057] In this specification, the acid value is a theoretical acid value, which is a value arithmetically determined based on the ethylenically unsaturated monomer having a carboxyl group and its content.

[0058] The weight average molecular weight of the alkali-soluble resin having a carboxyl group is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 10,000 to 30,000, from the viewpoint of developing properties and solubility in organic solvents.

[0059] In the present invention, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight obtained by GPC.

[0060] In this specification, Water 2690 (manufactured by Waters Corporation) is used as an apparatus for measuring the weight average molecular weight, and PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) is used as a column.

[0061] The content of the alkali-soluble resin having a carboxyl group is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, relative to 100 parts by mass of the black colorant.

[0062] In this case, when the content of the above-mentioned alkali-soluble resin having a carboxyl group is less than 1 part by mass, the developing characteristics are sometimes reduced. When the content of the above-mentioned alkali-soluble resin having a carboxyl group exceeds 200 parts by mass, since the concentration of the above-mentioned black colorant is relatively reduced, it is difficult to achieve the target color concentration (color density) as a film.

[0063] The alkali-soluble resin having a carboxyl group preferably does not contain any of primary, secondary, and tertiary amino groups, more preferably does not contain a quaternary amino group, and more preferably does not contain a basic group.

[0064] Furthermore, an alkali-soluble resin having a structure other than the block copolymer may be blended within a range not impairing the effects of the present invention.

[0065] (Photopolymerization initiator)

[0066] The resist composition for black matrices of the present invention contains a photopolymerization initiator.

[0067] The photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator that can generate free radicals or cations by irradiation with active energy rays such as ultraviolet rays and electron beams, and examples thereof include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-one]-1-(O-acetyl oxime), benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Photopolymerization initiators such as benzophenones such as benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylbenzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylbenzophenone, tert-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoquinidone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, and 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one, thioxanthones, anthraquinones, and triazines.

[0068] The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.

[0069] The content of the photopolymerization initiator is preferably 1 to 20% by mass as a mass fraction relative to the total solid content of the resist composition for a black matrix of the present invention.

[0070] (Organic Solvent)

[0071] The resist composition for black matrices of the present invention contains an organic solvent.

[0072] As the organic solvent, organic solvents conventionally used in the field of liquid crystal black matrix resists can be appropriately used.

[0073] Specifically, the organic solvent is a solvent at normal pressure (1.013×10 2 kPa) with a boiling point of 100 to 250°C, such as ester organic solvents, ether organic solvents, ether ester organic solvents, ketone organic solvents, aromatic hydrocarbon organic solvents, and nitrogen-containing organic solvents.

[0074] If a large amount of the organic solvent having a boiling point exceeding 250° C. is contained, the organic solvent may not be sufficiently evaporated during prebaking of the coating formed by applying the black matrix resist composition and may remain in the dried coating, thereby reducing the heat resistance of the dried coating.

[0075] Furthermore, if a large amount of the organic solvent having a boiling point of less than 100° C. is contained, uniform coating becomes difficult, and a coating film having excellent surface smoothness may not be obtained.

[0076] Specific examples of the organic solvent include: ether organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; ether ester organic solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; methyl isobutyl ketone, cyclohexanone, 2-[4-(2-methyl-1-oxo-1-yl)-1-piperidin-1-yl] ... Ketone organic solvents such as methyl-2-hydroxypropionate, ethyl-2-hydroxypropionate, ethyl-2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, and n-amyl formate; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in mixtures of two or more.

[0077] Among the above-mentioned organic solvents, in terms of solubility, dispersibility, coating properties, etc., diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-pentyl formate, etc. are preferred, and propylene glycol monomethyl ether acetate is more preferred.

[0078] (Oxazine compound)

[0079] The resist composition for a black matrix of the present invention contains an oxazine compound, and the oxazine compound is a compound represented by the following general formula (1) and / or (2).

[0080] The black matrix resist composition of the present invention contains the oxazine compound. Due to the high temperature during post-baking, the oxazine compound polymerizes to form a high molecular weight product. Therefore, even if the black colorant migrates within the coating film softened by the high temperature, the polymerized oxazine compound acts as a spacer, preventing the black colorants from contacting each other. Therefore, the black matrix resist composition of the present invention, which does not form a conductive structure, is expected to maintain a high surface resistance.

[0081] However, the present invention can also be interpreted without being limited to this mechanism of action.

[0082]

[0083] In the general formula (1), R 1 and R 2 represents an alkyl group or an aryl group optionally containing an unsaturated bond, and is optionally the same as or different from each other. 1 represents any one of the linking groups represented by the following formulae (3) to (5).

[0084]

[0085] -O-(5)

[0086] In the general formula (2), R 3 and R 4 represents an alkyl group or an aryl group optionally containing an unsaturated bond, and is optionally the same as or different from each other. 2 It is a divalent linking group.

[0087] R 1 and R 2 and R 3 and R 4 is an alkyl group or an aryl group which may contain an unsaturated bond.

[0088] The alkyl group may be, for example, linear, branched, or cyclic. Specific examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups, and alkyl groups optionally containing an unsaturated bond derived from cashew nut shell liquid (CNSL).

[0089] Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a biphenyl group, a naphthyl group, and an anthracenyl group.

[0090] X 2 It is a divalent linking group.

[0091] As the above-mentioned divalent linking group, in addition to the linking groups represented by the above-mentioned formulae (3) to (5), there can be mentioned: a straight-chain or branched alkylene group having 1 to 12 carbon atoms, a divalent linking group in which one or more -CH2- groups constituting the above-mentioned alkylene group are substituted by -O-, -S-, -NH-, a carbamate group, a urea group, an amide group, a siloxane bond optionally having a substituent, or -CO-, etc.

[0092] As the oxazine compound represented by the general formula (1), from the viewpoint of forming a black matrix having an excellent surface resistance value, R 1 and R 2 is an aryl group and X 1 It is any one of the linking groups represented by the above formulae (3) to (5).

[0093] Furthermore, the oxazine compound represented by the general formula (2) is preferably R 3 and R 4 is H and X 2 is methylenedioxy, or R 3 and R 4 is an alkyl group optionally containing an unsaturated bond derived from cashew nut shell liquid (CNSL) and X 2 For vinyl.

[0094] As a method for obtaining the above-mentioned oxazine compound, a well-known method can be adopted, for example, the method described in Japanese Patent Application Laid-Open No. 2000-178332, Japanese Patent Application Laid-Open No. 2003-344996, etc. can be adopted.

[0095] The content of the oxazine compound is preferably 0.1% by mass, more preferably 0.5% by mass, further preferably 1% by mass, particularly preferably 3% by mass, and most preferably 5% by mass, relative to the mass fraction of the total solid content of the black matrix resist composition of the present invention, from the viewpoint of appropriately forming a black matrix whose surface resist value does not decrease even after high-temperature and long-term post-baking.

[0096] In addition, from the viewpoint of appropriately ensuring the optical density of the black colorant derived from the black matrix, the upper limit of the content of the oxazine compound relative to the mass fraction of the total solid content of the black matrix resist composition of the present invention is preferably 30 mass %, more preferably 25 mass %, further preferably 20 mass %, and particularly preferably 15 mass %.

[0097] (Photopolymerizable compound)

[0098] The resist composition for a black matrix of the present invention preferably contains a photopolymerizable compound.

[0099] Examples of the photopolymerizable compound include monomers having one or two or more polymerizable unsaturated bonds in the molecule and oligomers having a photopolymerizable unsaturated bond.

[0100] As the above-mentioned monomer having one photopolymerizable unsaturated bond in the molecule, for example, alkyl methyl acrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; aryl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; aminoalkyl methacrylates or acrylates such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl acrylate; methacrylates or acrylates of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether; methacrylates or acrylates of polyalkylene glycol monoaryl ethers such as hexaethylene glycol monophenyl ether; isobornyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate, etc.

[0101] Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol tetramethacrylate. acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc.

[0102] As the oligomer having a photopolymerizable unsaturated bond, an oligomer obtained by appropriately polymerizing the above-mentioned monomers can be used.

[0103] The above-mentioned photopolymerizable compounds can be used alone or in combination of two or more.

[0104] The content of the photopolymerizable compound is preferably 3 to 50% by mass relative to the total solid content of the resist composition for a black matrix of the present invention.

[0105] (Pigment Dispersant)

[0106] The resist composition for a black matrix of the present invention preferably contains a pigment dispersant.

[0107] As the above-mentioned pigment dispersant, which is a pigment dispersant containing a basic group, anionic surfactants, polyester pigment dispersants containing a basic group, acrylic pigment dispersants containing a basic group, carbamate pigment dispersants containing a basic group, carbodiimide pigment dispersants containing a basic group, polymer pigment dispersants containing a basic group, etc. can be used.

[0108] These basic group-containing pigment dispersants may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining good pigment dispersibility, basic group-containing polymer pigment dispersants are preferred.

[0109] Specific examples of the above-mentioned basic group-containing polymer pigment dispersant include:

[0110] (1) Reaction products of an amino group and / or an imino group of a polyamine compound (e.g., poly(lower alkyleneamine) such as polyacrylamine, polyethyleneamine, polyethyleneimine, etc.) and at least one selected from the group consisting of polyesters, polyamides, and polyesteramides having a free carboxyl group (Japanese Patent Application Laid-Open No. 2001-59906);

[0111] (2) Reaction products of low molecular weight amino compounds such as poly(lower)alkylene imine and methyliminodipropylamine with polyesters having free carboxyl groups (Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application Laid-Open No. 01-311177);

[0112] (3) Reaction products obtained by sequentially reacting an alcohol such as methoxypolyethylene glycol, a polyester having one hydroxyl group such as caprolactone polyester, a compound having 2 to 3 isocyanate-reactive functional groups, or an aliphatic or heterocyclic hydrocarbon compound having an isocyanate-reactive functional group and a tertiary amino group with an isocyanate group of a polyisocyanate compound (Japanese Patent Application Laid-Open No. 02-612);

[0113] (4) a compound obtained by reacting a polyisocyanate compound and a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl group;

[0114] (5) a reaction product formed by adding a polyether chain to a low molecular weight amino compound;

[0115] (6) A reaction product formed by reacting a compound having an amino group with a compound having an isocyanate group (Japanese Patent Application Laid-Open No. 04-210220);

[0116] (7) A reaction product obtained by reacting a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group with a polyepoxide (Japanese Patent Application Laid-Open No. 09-87537);

[0117] (8) Reaction products of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound (Japanese Patent Application Laid-Open No. 09-194585);

[0118] (9) Copolymers of at least one methacrylate or acrylate selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octadecyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octadecyl acrylate, benzyl acrylate, etc., and at least one basic group-containing polymerizable monomer selected from acrylamide, methacrylamide, N-methanolamide, vinylimidazole, vinylpyridine, a monomer having an amino group and a polycaprolactone skeleton, and at least one polymerizable monomer selected from styrene, a styrene derivative, and other polymerizable monomers (Japanese Patent Application Laid-Open No. 01-164429);

[0119] (10) Carbodiimide pigment dispersants containing basic groups (International Publication No. WO04 / 000950);

[0120] (11) A block copolymer composed of a block having a basic group such as a tertiary amino group or a quaternary ammonium salt group and a block having no functional group (see Japanese Patent Application Laid-Open No. 2005-55814);

[0121] (12) Pigment dispersants obtained by Michael addition reaction of polycarbonate compounds with polyacrylamine (Japanese Patent Application Laid-Open No. 09-194585);

[0122] (13) Carbodiimide compounds each having at least one polybutadiene chain and a basic nitrogen-containing group (Japanese Patent Application Laid-Open No. 2006-257243);

[0123] (14) Carbodiimide compounds each having at least one side chain having an amide group and a basic nitrogen-containing group in the molecule (Japanese Patent Application Laid-Open No. 2006-176657);

[0124] (15) A polyurethane compound having a constituent unit having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized by a quaternizing agent (Japanese Patent Application Laid-Open No. 2009-175613);

[0125] (16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in its molecule with active hydrogen of a compound having a carbazole ring and / or an azobenzene skeleton and having active hydrogen in its molecule, wherein the number of carbazole rings and azobenzene skeletons is 15 to 85% relative to the total number of isocyanate groups derived from the isocyanate compound having an isocyanurate ring, urethane bonds, and urea bonds formed by the reaction of the isocyanate groups and active hydrogen in the molecule of the compound (Japanese Patent Application No. 2009-220836);

[0126] (17) Graft copolymers obtained by introducing polyether or polyester side chains into acrylate polymers having amino groups; etc.

[0127] Among the above-mentioned basic group-containing polymer pigment dispersants, more preferred are basic group-containing carbamate polymer pigment dispersants, basic group-containing polyester polymer pigment dispersants, and basic group-containing acrylic polymer pigment dispersants. Even more preferred are amino group-containing carbamate polymer pigment dispersants, amino group-containing polyester polymer pigment dispersants, and amino group-containing acrylic polymer pigment dispersants. Among the above-mentioned basic group-containing polymer pigment dispersants, particularly preferred are pigment dispersants containing at least one basic group (amino group) selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains.

[0128] The content of the pigment dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, relative to 100 parts by mass of the black colorant.

[0129] (Other additives)

[0130] The resist composition for a black matrix of the present invention may appropriately contain various additives such as a thermal polymerization inhibitor, a UV absorber, and an antioxidant, as needed.

[0131] (Method for producing a resist composition for a black matrix)

[0132] The method for producing the black matrix resist composition of the present invention can be, for example, prepared by the following method: adding and mixing the above-mentioned black colorant, the above-mentioned organic solvent, and the above-mentioned pigment dispersant as needed to prepare a pigment dispersion; then, adding the remaining materials to the above-mentioned pigment dispersant, and stirring and mixing using a stirring device or the like to obtain the above-mentioned composition.

[0133] The stirring and mixing method is not particularly limited, and a known method of stirring and mixing using an ultrasonic disperser, a high-pressure emulsifier, a bead mill, a three-roll mill, a sand mill, a kneader, or the like can be used.

[0134] In addition, the oxazine compound may be added during the preparation of the pigment dispersion, or may be added together with the remaining materials after the preparation of the pigment dispersion.

[0135] Black Matrix

[0136] The black matrix of the present invention is formed using the resist composition for a black matrix of the present invention.

[0137] There is no particular limitation on the method for forming the black matrix of the present invention. For example, the anti-etching composition for the black matrix of the present invention can be coated on a transparent substrate, dried to form a coating film, and then a photomask is placed on the coating film. The image is exposed and developed through the photomask, and a black matrix is ​​formed by photocuring or the like as needed.

[0138] As the method for coating, drying, exposing, and developing the resist composition for a black matrix of the present invention, a well-known method can be appropriately selected.

[0139] As the transparent substrate, a well-known transparent substrate such as a glass substrate or a plastic substrate can be appropriately selected and used.

[0140] The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm.

[0141] By setting the thickness of the coating film to be within the above-mentioned range, a predetermined pattern can be appropriately developed and a predetermined optical density can be appropriately provided.

[0142] For the black matrix of the present invention, the black matrix resist composition of the present invention was coated on a glass substrate (Corning 1737), pre-baked at 100°C for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated luminance 400mJ / cm 2 ), and then post-baking at 230°C for 30 minutes to form an optical density (OD value) of 3.0 or more, more preferably 3.5 or more, further preferably 4.0 or more, and particularly preferably 4.5 or more when forming a resist pattern with a thickness of 1 μm.

[0143] When the optical density (OD value) is 3.0 or more, it can be said that the shielding property is sufficient.

[0144] The optical density (OD value) is a value measured using a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth) by forming a resist pattern with only a solid portion of 1 μm.

[0145] For the black matrix of the present invention, the black matrix resist composition of the present invention was coated on a glass substrate (Corning 1737), pre-baked at 100°C for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated luminance 400mJ / cm 2 ), and then post-baking was performed at 230°C for 30 minutes. The surface resistance value when forming a resist pattern with a thickness of 1 μm was preferably 5.0×10 13 Ω / □ or more, more preferably 1.0×10 14 Ω / □ or more, more preferably 5.0×10 14 Ω / □ or more, particularly preferably 1.0×10 15 Ω / □ or more, and most preferably 3.0×10 15 Ω / □ or more.

[0146] The surface resistance value can be measured using "Main unit: micro ammeter R8340; Option: shield box R12702A" (both manufactured by ADVANCE Co., Ltd.).

[0147] For the black matrix of the present invention, the black matrix resist composition of the present invention was coated on a glass substrate (Corning 1737), pre-baked at 100°C for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated luminance 400mJ / cm 2 ), and then post-baking was performed at 230°C for 3 hours. The surface resistance value when forming a resist pattern with a thickness of 1 μm was preferably 1.0×10 13 Ω / □ or more, more preferably 5.0×10 13 Ω / □ or more, more preferably 1.0×10 14 Ω / □ or more, particularly preferably 5.0×10 14 Ω / □ or more.

[0148] Since the resist composition for black matrices and the black matrix of the present invention have the above-mentioned properties, they can be suitably used as a black matrix for image display devices, touch panels, and the like.

[0149] Effects of the Invention

[0150] According to the present invention, a resist composition for a black matrix can be provided, which can form a black matrix whose surface resistance value does not decrease even after post-baking at a high temperature and for a long time. DETAILED DESCRIPTION

[0151] Below, give embodiment and specifically describe to the present invention, as long as do not depart from the purpose and scope of application of the present invention, then the present invention is not limited by these embodiment.In addition, unless otherwise stated, the "part" and "%" described in the present embodiment represent "mass part" and "mass %" respectively.

[0152] Various materials used in the following examples and comparative examples are as follows.

[0153] Black colorant

[0154] Carbon black (product name "SPECIAL BLACK 250", average primary particle size 56 nm, pH 3.0, manufactured by Orion Engineered Carbons Co., Ltd.)

[0155] <Alkali-soluble resin having a carboxyl group>

[0156] Resin 1: benzyl methacrylate / methacrylic acid block copolymer (weight average molecular weight 23,000, acid value 100 mgKOH / g)

[0157] Resin 2: benzyl methacrylate / methacrylic acid block copolymer (weight average molecular weight 23,000, acid value 50 mgKOH / g)

[0158] Resin 3: benzyl methacrylate / methacrylic acid block copolymer (weight average molecular weight 23,000, acid value 150 mgKOH / g)

[0159] Resin 4: benzyl methacrylate / methacrylic acid block copolymer (weight average molecular weight 5000, acid value 100 mgKOH / g)

[0160] Resin 5: benzyl methacrylate / methacrylic acid block copolymer (weight average molecular weight 50,000, acid value 100 mgKOH / g)

[0161] <Photopolymerization initiator>

[0162] Omnirad907 (product name “Omnirad907”, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by IGM Resins BV)

[0163] Organic solvents

[0164] PGMEA (propylene glycol monomethyl ether acetate)

[0165] <Oxazine compounds>

[0166] (Oxazine compound 1)

[0167] In the above general formula (2), R 3 and R 4 H, X 2 An oxazine compound represented by a methylenedioxy group (trade name "JBZ-OP100N", manufactured by JFE Chemical Industries, Ltd.)

[0168] (Oxazine compound 2)

[0169] In the above general formula (1), R 1 and R 2 is phenyl, and X is synthesized by a well-known method (method described in Japanese Patent Application Laid-Open No. 2000-178332, etc.) 1 It is an oxazine compound represented by the above formula (3).

[0170] (Oxazine compound 3)

[0171] In the above general formula (2), R 3 and R 4 is an alkyl group optionally containing an unsaturated bond derived from cashew nut shell liquid (CNSL), X 2 An oxazine compound represented by a vinyl group (trade name "CR-276", manufactured by Tohoku Chemical Industry Co., Ltd.)

[0172] (Oxazine compound 4)

[0173] In the above general formula (1), R 1 and R 2 is phenyl, and X is synthesized by a well-known method (method described in Japanese Patent Application Laid-Open No. 2000-178332, etc.) 1 It is an oxazine compound represented by the above formula (4).

[0174] (Oxazine compound 5)

[0175] In the above general formula (1), R 1 and R 2 is phenyl, and X is synthesized by a well-known method (method described in Japanese Patent Application Laid-Open No. 2000-178332, etc.) 1 It is an oxazine compound represented by the above formula (5).

[0176] (Oxazine compound 6)

[0177] In the above general formula (1), R 1 and R 2 is phenyl, and X is synthesized by a well-known method (method described in Japanese Patent Application Laid-Open No. 2000-178332, etc.) 1 It is an oxazine compound represented by a methylene group.

[0178] (Oxazine compound 7)

[0179] In the above general formula (1), R 1 and R 2 is phenyl, and X is synthesized by a well-known method (method described in Japanese Patent Application Laid-Open No. 2000-178332, etc.) 1It is an oxazine compound represented by a 2-propylene group.

[0180] <Photopolymerizable compounds>

[0181] DPHA (dipentaerythritol hexaacrylate)

[0182] Pigment dispersants

[0183] 50.0 parts of a polycarbodiimide compound having an isocyanate group and a carbodiimide equivalent of 316 and 115.7 parts of poly(3-methylpentyl adipate)diol having a molecular weight of 1000 were placed in a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a stirring rod, and a thermometer. The mixture was maintained at approximately 100° C. for 5 hours to allow the isocyanate groups to react with the hydroxyl groups. Subsequently, 84.6 parts of a ring-opening polymer of polycaprolactone having a molecular weight of 2000 and a carboxyl group at the terminal was added. The mixture was maintained at approximately 100° C. for 2 hours to allow the carbodiimide groups to react with the carboxyl groups. Then, 375.5 parts of propylene glycol monomethyl ether acetate was added to prepare a pigment dispersant solution having a number average molecular weight of approximately 4200 and a carbodiimide equivalent of 1583 (solid content 40% by mass).

[0184] <Preparation of Pigment Dispersion>

[0185] The above-mentioned black colorant, a solution of a pigment dispersant (solid content: 40% by mass), and an organic solvent were mixed to have the composition shown in Table 1, and kneaded overnight using a bead mill to prepare a pigment dispersion.

[0186] [Table 1]

[0187] Black colorant 22.5 Pigment dispersant solution (solid content 40% by mass) 22.5 organic solvents 55.0 Total (mass %) 100.0

[0188] The pigment dispersion and other materials (oxazine compounds 1 to 7, photopolymerizable compound, alkali-soluble resin, photopolymerization initiator, and organic solvent) were uniformly mixed using a high-speed stirrer to form the composition shown in Table 2, and then filtered through a filter with a pore size of 3 μm to obtain the black matrix resist composition of the embodiment and comparative example.

[0189] <Evaluation Test>

[0190] (OD value)

[0191] Each of the pigment dispersion resist compositions for black matrices of the examples and comparative examples was applied to a glass substrate (Corning 1737) using a spin coater to a film thickness of 1 μm, pre-baked at 100° C. for 3 minutes, and then exposed using a high-pressure mercury lamp (UV integrated irradiance 400 mJ / cm 2 ), and then post-baked at 230° C. for 30 minutes to prepare a black resist pattern consisting only of a solid portion.

[0192] The optical density (OD value) of each prepared black resist pattern was measured using a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth Co., Ltd.).

[0193] (Surface resistance value 1)

[0194] A black resist pattern was prepared in the same manner as in the above-mentioned measurement of the OD value.

[0195] The surface resistance value of each prepared black resist pattern was measured using "Main unit: micro ammeter R8340; Option: shield box R12702A" (both manufactured by ADVANCE Co., Ltd.).

[0196] (Surface resistance value 2)

[0197] Each of the pigment dispersion resist compositions for black matrices of the examples and comparative examples was applied to a glass substrate (Corning 1737) using a spin coater to a film thickness of 1 μm, pre-baked at 100° C. for 3 minutes, and then exposed using a high-pressure mercury lamp (UV integrated irradiance 400 mJ / cm 2 ), and then post-baked at 230° C. for 3 hours to prepare a black resist pattern consisting only of a solid portion.

[0198] The surface resistance value of each prepared black resist pattern was measured using "Main unit: micro ammeter R8340; Option: shield box R12702A" (both manufactured by ADVANCE Co., Ltd.).

[0199] [Table 2]

[0200]

[0201] The examples confirmed that by using a black matrix resist composition containing a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent, and a specific oxazine compound, a black matrix having excellent shielding properties and whose surface resistance does not decrease even after high-temperature and long-term post-baking can be formed.

[0202] On the other hand, it was confirmed that in Comparative Example 1, which did not use an oxazine compound, a black matrix having a sufficient surface resistance value could not be formed. In Comparative Examples 2 and 3, which used oxazine compounds other than the specified oxazine compounds, the surface resistance value decreased when high-temperature and long-term post-baking was applied.

[0203] Industrial Applicability

[0204] According to the present invention, a resist composition for a black matrix can be provided, which can form a black matrix whose surface resistance value does not decrease even after post-baking at a high temperature and for a long time.

Claims

1. A resist composition for black matrix, characterized in that The resist composition for a black matrix comprises a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent, and an oxazine compound. The oxazine compound is a compound represented by the following general formula (1) and / or (2): The content of the oxazine compound is 0.1% to 15% by mass based on the mass fraction of the total solid content. In the general formula (1), R 1 and R 2 represents an alkyl group or an aryl group optionally containing an unsaturated bond, which are optionally the same as or different from each other; X 1 represents any one of the linking groups represented by the following formulae (3) to (5), In the general formula (2), R 3 and R 4 represents an alkyl group or an aryl group optionally containing an unsaturated bond, which are optionally the same as or different from each other; X 2 It is a divalent linking group, which is a linking group represented by the above formulas (3) to (5), a linear or branched alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- groups constituting the alkylene group are substituted by -O-, -S-, -NH-, a carbamate group, a urea group, an amide group, a siloxane bond optionally having a substituent, or -CO-. 2 . A black matrix formed from the resist composition for a black matrix according to claim 1 .

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