Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix

Abstract

The technical problem to be solved by the present invention is to provide a pigment dispersion composition for a black matrix, with which it is possible to form a black matrix having excellent fine line adhesion when forming a black matrix, and also having excellent optical density as an optical density as an optical density as a low reflectance as a low Y value and a low L * value. [Solution] A pigment dispersion composition for a black matrix, which contains a pigment, a pigment dispersant and a binder resin, the pigment including a black pigment and a blue pigment, the black pigment including carbon black, and the content of the black pigment being 82-95% by mass (inclusive) relative to the total mass of the pigment.

Description

Technical Field

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

[0002] A light-shielding film (black matrix) is provided in the gaps between colored patterns in the screen display area and the edges around the display area in an image display device using liquid crystal, plasma, etc., and also on the external light side of TFT in a liquid crystal display using TFT.

[0003] 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 mixing of different color lights from entering the screen, thereby helping to improve display characteristics (contrast and color purity).

[0004] For example, a color filter (also called a color filter, etc.) for converting white light from a backlight source of a liquid crystal display device into colored light is 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 a glass or plastic sheet having a black matrix.

[0005] In addition, even in a touch panel that aligns an image display device with a position input device, a filter formed with a black matrix as a light-shielding film is also used, and it is usually formed on the side opposite to the sensor substrate through a glass cover (protective sheet). However, as the demand for lightweight touch panels increases, a technology for simultaneously forming a light-shielding film and a touch sensor on the same side of a glass cover is being developed to achieve even lighter weight.

[0006] As a method for forming such a black matrix, for example, a photolithography method (pigment method) using a black matrix composition containing a pigment is utilized. The pigment mainly uses carbon black with excellent light-shielding properties. However, for a liquid crystal display device equipped with a filter substrate having a black matrix with black pigments such as carbon black as a light-shielding material, the deterioration of outdoor visibility caused by external light reflection can become a problem.

[0007] In this context, a low reflectivity (low Y value, low L * value), it is difficult to prepare a black matrix with a dispersion liquid for a black matrix using only a black pigment as a coloring material.

[0008] Therefore, a black matrix dispersion liquid containing not only a black pigment but also a pigment other than black as a coloring material has been studied.

[0009] For example, Patent Document 1 discloses a pigment dispersion composition for a black matrix, which contains at least (A) a black pigment and contains (B) a non-black pigment as a light-shielding material, and also contains (C) an alkali-soluble resin, (D) a polyfunctional acrylic monomer, (E) a photo-radical polymerization initiator, and (F) an organic solvent; it is characterized in that the weight ratio of (A) the black pigment to the total weight of the light-shielding material is 60% by weight or more and 95% by weight or less, and as (A) the black pigment, it contains (A-1) carbon black, (B) the non-black pigment, (B-1) a yellow pigment, and (B-2) a red pigment.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2013-205474 Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] Patent Document 1 discloses that it contains a yellow pigment and a red pigment as non-black pigments.

[0015] However, in recent years, there has been a demand for a black matrix with a lower reflectance (low Y value, low L * value), and there is still room for improvement.

[0016] In addition, in recent years, there has been a demand for a black matrix with excellent fine line adhesion and excellent OD value (optical density) when forming a black matrix.

[0017] Therefore, an object of the present invention is to provide a pigment dispersion composition for a black matrix, from which a black matrix with excellent fine line adhesion and excellent OD value (optical density) and low reflectance (low Y value, low L * value) can be formed when forming a black matrix.

[0018] Means for Solving the Problems

[0019] The present invention is a pigment dispersion composition for a black matrix, which contains a pigment, a pigment dispersant, and a binder resin. The above-mentioned pigment contains a black pigment and a blue pigment. The above-mentioned black pigment contains carbon black, and the content of the above-mentioned black pigment is 82% by mass or more and 95% by mass or less relative to the total mass of the above-mentioned pigment.

[0020] The pigment dispersion composition for a black matrix of the present invention further contains a pigment derivative, and the above-mentioned pigment derivative is preferably a sulfide of copper phthalocyanine.

[0021] In addition, the above blue pigment preferably contains at least one selected from C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 16, and C.I. Pigment Blue 60.

[0022] In addition, the above black pigment preferably contains acid black.

[0023] In addition, it is preferable that the above binder resin is an alkali-soluble Cardo resin (also referred to as "Cardo resin").

[0024] In addition, the present invention also relates to a resist composition for a black matrix, which contains the pigment dispersion composition for a black matrix of the present invention, a photopolymerizable compound, and a photopolymerization initiator.

[0025] In addition, the present invention also relates to a black matrix formed from the resist composition for a black matrix of the present invention.

[0026] Advantages of the Invention

[0027] The present invention can provide a pigment dispersion composition for a black matrix, from which a black matrix having excellent fine line adhesion when forming the black matrix, and having excellent OD value (optical density) and low reflectance (low Y value, low L value) can be formed. * value). Detailed Embodiments

[0028] <Pigment Dispersion Composition for Black Matrix>

[0029] The pigment dispersion composition for a black matrix of the present invention contains a pigment, a pigment dispersant, and a binder resin. The above pigment contains a black pigment and a blue pigment. The above black pigment contains carbon black, and the content of the above black pigment is 82% by mass or more and 95% by mass or less relative to the total mass of the above pigment.

[0030] When the pigment dispersion composition for a black matrix of the present invention contains a blue pigment, compared with carbon black alone, it presents a blueish hue, the blackness increases (low L value), and ultraviolet absorption is suppressed. Therefore, it is considered that internal curing is promoted during UV exposure, improving fine line adhesion. * value), suppressing ultraviolet absorption, and thus it is considered that internal curing is promoted during UV exposure to improve fine line adhesion.

[0031] In addition, compared with using other organic pigments in combination, the blue pigment is considered to have more excellent OD value, high affinity with carbon black, and will become a spacer for carbon black, thereby contributing to low reflectance (low Y value) by reflecting light.

[0032] Here, the present invention is not limited to being explained by the above mechanism.

[0033] Next, each component constituting the pigment dispersion composition for a black matrix of the present invention will be described in detail.

[0034] [Pigment]

[0035] (Black pigment)

[0036] The pigment dispersion composition for a black matrix of the present invention contains a black dye.

[0037] The black pigment contains carbon black.

[0038] As the above carbon black, acidic carbon black or neutral carbon black is more preferable.

[0039] The acidic carbon black and the neutral carbon black will be described.

[0040] Carbon black can be roughly classified into acidic carbon black and neutral carbon black according to the surface structure. Acidic carbon black refers to a carbonaceous substance that has been originally oxidized or artificially oxidized and shows acidity when mixed and boiled with distilled water. On the other hand, neutral carbon black is known to show neutral or a higher pH when mixed and boiled with distilled water.

[0041] As the above black pigment, the average primary particle size is preferably 20 to 50 nm, and more preferably 25 to 45 nm.

[0042] By making the average primary particle size of the above black dye fall within the above range, the line width of the formed black matrix can be maintained at an appropriate line width, and the fine line adhesion and the surface resistance value can be more appropriately improved. In addition, storage stability can also be appropriately imparted.

[0043] In addition, the above average primary particle size is the value of the arithmetic mean diameter based on electron microscope observation.

[0044] As the acidic carbon black, the pH is preferably in the range of 2.0 to 4.0. Specifically, examples include: Raven 1080 manufactured by Columbian Chemicals (average primary particle size of 28 nm, pH 2.4), Raven 1100 (average primary particle size of 32 nm, pH 2.9); MA-7 manufactured by Mitsubishi Chemical Corporation (average primary particle size of 24 nm, pH 2.5), MA-8 (average primary particle size of 24 nm, pH 3.0), MA-100 (average primary particle size of 22 nm, pH 3.5); SpecialBlack250 (average primary particle size 56 nm, pH 3.0), SpecialBlack350 (average primary particle size of 31 nm, pH 3.0), SpecialBlack550 (average primary particle size of 25 nm, pH 4.0), NEROX 305 (average primary particle size of about 28 nm, pH about 2.8), NEROX 3500 (average primary particle size of about 31 nm, pH about 2.5), etc. manufactured by Orion Engineered Carbons.

[0045] As the neutral carbon black, the pH is preferably in the range of 8.0 to 10.0. Specifically, examples include: Printex 25 (average primary particle size of 56 nm, pH 9.5), Printex 35 (average primary particle size of 31 nm, pH 9.5), Printex 65 (average primary particle size of 21 nm, pH 9.5) manufactured by Orion Engineered Carbons; MA#20 (average primary particle size of 40 nm, pH 8.0), MA#40 (average primary particle size of 40 nm, pH 8.0), MA#30 (average primary particle size of 30 nm, pH 8.0), etc. of Mitsubishi Chemical Corporation.

[0046] In addition, 1 g of carbon black can be added to 20 ml of carbon dioxide-free distilled water (pH 7.0) and mixed with a magnetic stirrer to prepare an aqueous suspension, and the above pH is measured at 25 °C using a glass electrode (German industrial standard DIN ISO 787 / 9).

[0047] From the viewpoints of reflectance and OD when forming the black matrix, the content of the above black pigment is 82% by mass or more and 95% by mass or less relative to the total mass of the pigments.

[0048] The content of the above black pigment is preferably 82% by mass or more and 95% by mass or less, more preferably 85% by mass or more and 92% by mass or less, and most preferably 90% by mass, relative to the total mass of the pigments.

[0049] (Blue pigment)

[0050] The pigment dispersion composition for a black matrix of the present invention contains a blue dye.

[0051] Examples of the above blue pigments include: C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.

[0052] As the above blue pigment, from the viewpoints of dispersion stability and developability, it preferably contains at least one selected from C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 16, and C.I. Pigment Blue 60.

[0053] From the viewpoints of reflectance (low Y value, low L * value) and OD when forming the black matrix, the content of the above blue pigment is 5% by mass or more and 18% by mass or more, more preferably 5% by mass or more and 15% by mass or less, further preferably 12% by mass or less, and most preferably 10% by mass, relative to the total mass of the above pigments.

[0054] (Other)

[0055] From the viewpoint of low reflectance (low Y value, low L * value), the above pigment preferably does not contain pigments other than the above black pigment and blue pigment (composed of black pigment and blue pigment).

[0056] (Content of pigment)

[0057] As the content of the above dye, from the viewpoints of light-shielding property and pigment dispersibility when forming the black matrix, in terms of mass fraction relative to the total solid content of the pigment dispersion composition for a black matrix of the present invention, it is preferably 5% by mass to 85% by mass, more preferably 10% by mass to 80% by mass.

[0058] (Pigment dispersant)

[0059] The pigment dispersion composition for a black matrix of the present invention contains a pigment dispersant.

[0060] In addition, it is preferable that the amine value of the above pigment dispersant is 10 to 200 mgKOH / g.

[0061] By making the amine value of the above pigment dispersant within the above range, the viscosity of the pigment dispersion composition for a black matrix can be lowered, and the carbon black in the coating film can reach a high concentration, so that a black matrix with excellent optical density can be obtained.

[0062] In addition, it is preferable that the amine value of the above pigment dispersant is 20 to 150 mgKOH / g.

[0063] In addition, the amine value is the value representing the total amount of free base and base, and it is the value expressed in milligrams (mg) of potassium hydroxide equivalent to the hydrochloric acid required to neutralize 1 g of the sample.

[0064] As the above pigment dispersant, which is a pigment dispersant containing a basic group, an anionic surfactant, a polyester-based pigment dispersant containing a basic group, an acrylic-based pigment dispersant containing a basic group, a urethane-based pigment dispersant containing a basic group, a carbodiimide-based pigment dispersant containing a basic group, a polymer pigment dispersant, etc. can be used.

[0065] These pigment dispersants containing a basic group can be used alone or in combination of two or more. Among them, from the viewpoint of obtaining good pigment dispersibility, a polymer pigment dispersant containing a basic group is preferred.

[0066] As a specific example of the above polymer pigment dispersant containing a basic group, the following can be cited:

[0067] (1) The reaction product of the amino group and / or imino group of a polyamine compound (such as poly(alkyleneimine) such as polyallylamine, polyvinylamine, polyethylene polyimine, etc.) and at least one selected from the group consisting of a polyester, a polyamide, and a polyester amide having a free carboxyl group (Japanese Patent Laid-Open No. 2001-59906);

[0068] (2) The reaction product of a poly(lower) alkyleneimine, a low molecular weight amino compound such as methyliminobispropylamine, and a polyester having a free carboxyl group (Japanese Patent Laid-Open No. 54-37082, Japanese Patent Laid-Open No. 01-311177);

[0069] (3) The reaction product formed by sequentially reacting an alcohol such as methoxypolyethylene glycol, a polyester having one hydroxyl group such as ε-caprolactone polyester, a compound having 2 to 3 isocyanate-reactive functional groups, and an aliphatic or heterocyclic hydrocarbon compound having an isocyanate-reactive functional group and a tertiary amino group with the isocyanate group of a polyisocyanate compound (Japanese Patent Laid-Open No. 02-612);

[0070] (4) A compound obtained by reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group;

[0071] (5) The reaction product obtained by adding a low molecular weight amino compound to a polyether chain;

[0072] (6) A reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group (Japanese Patent Laid-Open No. 04-210220);

[0073] (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 compound (Japanese Patent Laid-Open No. 09-87537);

[0074] (8) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one terminal with a polyamine compound (Japanese Patent Laid-Open No. 09-194585);

[0075] (9) A copolymer of at least one selected from methacrylates or acrylates such as 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 selected from polymerizable monomers containing basic groups such as acrylamide, methacrylamide, N-hydroxymethylamide, vinylimidazole, vinylpyridine, monomers having an amino group and a polycaprolactone skeleton, etc. and at least one selected from styrene, styrene derivatives, and other polymerizable monomers (Japanese Patent Laid-Open No. 01-164429);

[0076] (10) A carbodiimide-based pigment dispersant containing a basic group (WO2004 / 000950);

[0077] (11) A block copolymer composed of a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no functional group (see the description in Japanese Patent Laid-Open No. 2005-55814);

[0078] (12) A pigment dispersant obtained by subjecting polyallylamine and a polycarbonate compound to a Michael addition reaction (Japanese Patent Laid-Open No. 09-194585);

[0079] (13) A carbodiimide-based compound having at least one polybutadiene chain and a basic nitrogen-containing group respectively (Japanese Patent Laid-Open No. 2006-257243);

[0080] (14) A carbodiimide-based compound having at least one side chain having an amide group and a basic nitrogen-containing group respectively in the molecule (Japanese Patent Laid-Open No. 2006-176657);

[0081] (15) A polyurethane compound having a structural unit having an ethylene oxide chain and a propylene oxide chain and an amino group quaternized with a quaternizing agent (Japanese Patent Laid-Open No. 2009-175613);

[0082] (16) A compound obtained by reacting the isocyanate groups of an isocyanate compound having an isocyanurate ring in the molecule with the active hydrogen groups of a compound having an active hydrogen group in the molecule and having a carbazole ring and / or an azobenzene skeleton, wherein the number of carbazole rings and azobenzene skeletons in the molecule of the compound relative to the total of the urethane bonds and urea bonds formed by the reaction of the isocyanate groups derived from the isocyanate compound having an isocyanurate ring with the active hydrogen groups is 15 to 85% (Japanese Patent Laid-Open No. 2010-107965);

[0083] (17) A graft copolymer in which a polyether or polyester side chain is introduced into an acrylate polymer having an amino group.

[0084] Among the above pigment dispersants, from the viewpoints of dispersion stability, developability, and reflectance, a block copolymer composed of a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no functional group is preferred.

[0085] As the above block copolymer, specifically, a block copolymer composed of an A block having at least one of a quaternary ammonium base and an amino group in the side chain and a B block having no quaternary ammonium base and amino group is preferred, and more preferably at least one of an A-B block copolymer and a B-A-B block copolymer.

[0086] The amine value of the above block copolymer is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g.

[0087] In addition, the amine value is a value represented by the milligram (mg) number of KOH corresponding to the molar equivalent of the acid required to neutralize the amino groups in 1 g of the acrylic block copolymer.

[0088] The molecular weight of the above block copolymer is preferably such that the polystyrene-converted weight-average molecular weight (Mw) measured by GPC is 1000 to 40000, more preferably 2000 to 20000.

[0089] Examples of commercially available products of the above pigment dispersant include BYK-LPN21116, BYK-2000, BYK-LPN6919, BYK-LPN21324, and BYK-LPN22102 (all manufactured by BYK-Chemie).

[0090] As the content of the above pigment dispersant, relative to 100 parts by mass of the above black dye, it is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass.

[0091] (Binder resin)

[0092] The pigment dispersion composition for a black matrix of the present invention contains a binder resin.

[0093] Examples of the above binder resin include thermosetting resins, thermoplastic resins, photopolymerizable compounds, alkali-soluble resins, etc. These can be used alone or in combination of two or more.

[0094] Examples of the above thermosetting resin or thermoplastic resin include: butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, phenolic resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea-formaldehyde resin (urea resin), cardo resin, etc.

[0095] Examples of the above photopolymerizable compound include monomers having one or more photopolymerizable unsaturated bonds in the molecule, oligomers having photopolymerizable unsaturated bonds, etc.

[0096] Examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, aralkyl methacrylates or acrylates such as benzyl methacrylate, benzyl acrylate, alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate, butoxyethyl acrylate, aminoalkyl methacrylates or acrylates such as N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, methacrylates or acrylates of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, methacrylates or acrylates of polyalkylene glycol monoaryl ethers such as hexapolyethylene glycol monophenyl ether, isobornyl methacrylate or acrylate, glycerol methacrylate or acrylate, 2-hydroxyethyl methacrylate or acrylate, etc.

[0097] As the monomer having two or more photopolymerizable unsaturated bonds in the molecule, for example, 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, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, epoxy methacrylate, 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, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexacrylate, dipentaerythritol pentacrylate, epoxy acrylate, etc. can be used.

[0098] As the oligomer having a photopolymerizable unsaturated bond, an oligomer obtained by appropriately polymerizing the above monomers can be used.

[0099] The above adhesive resin can be used alone or in combination of two or more.

[0100] The above alkali-soluble resin will be described later.

[0101] From the viewpoints of dispersion stability and developability when forming a black matrix, the above adhesive resin is preferably an alkali-soluble cardo resin.

[0102] In addition, in this specification, the meaning of the above cardo resin refers to a resin having a skeleton structure obtained by bonding two aromatic rings to the carbon atoms in the ring.

[0103] As the above cardo resin, for example, an epoxy (meth)acrylate acid adduct having a fluorene skeleton, which is an addition product of a fluorene epoxy (meth)acrylate derivative and a dicarboxylic anhydride and / or a tetracarboxylic dianhydride, can be mentioned.

[0104] In addition, in this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid, and (meth)acrylate means acrylate and / or methacrylate.

[0105] From the viewpoints of pigment dispersibility and fine line adhesion, the acid value of the above-mentioned cardo resin is preferably 5 to 300 mgKOH / g, more preferably 5 to 250 mgKOH / g, still more preferably 10 to 200 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g.

[0106] In addition, in this specification, the above acid value is a theoretical acid value, which is a value calculated arithmetically based on the ethylenically unsaturated monomer having a carboxyl group and its content.

[0107] The weight average molecular weight (Mw) of the above-mentioned cardo resin is preferably 1000 to 100000, more preferably 1500 to 50000, still more preferably 2000 to 30000.

[0108] In addition, in this specification, Water2690 (manufactured by Waters Corporation) was used as the device for measuring the weight average molecular weight, and PLgeL 5μm MIXED-D (manufactured by Agilent Technologies) was used as the column.

[0109] As commercially available products of the above-mentioned cardo resin, for example, WR-301 (manufactured by ADEKA Corporation) can be cited.

[0110] As the content of the above binder resin, the mass fraction relative to the total solid content of the pigment dispersion composition for a black matrix of the present invention is preferably 3 to 50 mass%.

[0111] (Pigment derivative)

[0112] The pigment dispersion composition for a black matrix of the present invention preferably further contains a pigment derivative.

[0113] As the above pigment derivative, at least one selected from the group consisting of a pigment derivative having an acid group (acid radical / acidic group) and a pigment derivative having an acid group can be cited.

[0114] As the above pigment derivative having an acid group and pigment derivative having an acid group, phthalocyanine pigment derivatives which are sulfonates of copper phthalocyanine, anthraquinone pigment derivatives having an acid group, naphthalene pigment derivatives having an acid group, pigment derivatives having a diketopyrrolopyrrole skeleton, etc. can be exemplified.

[0115] Among them, the sulfonate of copper phthalocyanine is preferred from the viewpoints of high affinity with the conjugated double bond of the above black dye and being able to appropriately impart dispersibility.

[0116] Specific examples of the sulfonated product of the above copper phthalocyanine include Solsperse 5000S and Solsperse 12000S manufactured by Lubrizol Corporation, BYK-SYNERGIST 2100 manufactured by BYK Chemie GmbH, etc.

[0117] As the content of the above pigment derivative, it is preferably 0 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the above black pigment.

[0118] (Organic solvent)

[0119] The pigment dispersion composition for a black matrix of the present invention preferably contains an organic solvent.

[0120] As the above organic solvent, an organic solvent conventionally used in the field of liquid crystal black matrix resists can be appropriately used.

[0121] Specific examples of the above 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; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone; ester organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, and n-amyl formate; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These can be used alone or in combination of two or more.

[0122] Among the above organic solvents, from the viewpoints of solubility, dispersibility, coatability, etc., diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and n-amyl formate are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferred.

[0123] (Method for producing the pigment dispersion composition for a black matrix)

[0124] The manufacturing method of the pigment dispersion composition for a black matrix of the present invention is not particularly limited. For example, by mixing and grinding (ink grinding treatment) a black pigment, a blue pigment, a pigment dispersant, a binder resin, and optionally a pigment derivative and an organic solvent as needed, the pigment dispersion composition for a black matrix of the present invention can be manufactured.

[0125] As the above-mentioned black pigment, blue pigment, pigment dispersant, binder resin, and if necessary, a pigment derivative and an organic solvent as needed, the above materials can be used.

[0126] As the method of the above mixing and grinding (ink grinding treatment), it is only necessary to add the above various components for mixing and grinding. As the method of performing the above grinding, there is no particular limitation. For example, a bead mill, a Ready mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a DYNO-MILL, a high-speed disperser (DISPERMAT), an SC mill, a high-pressure homogenizer (Nanomizer), etc. can be used, and mixing and grinding are performed by a well-known method.

[0127] <Resist composition for a black matrix>

[0128] The present invention also relates to a resist composition for a black matrix obtained from the pigment dispersion composition for a black matrix of the present invention.

[0129] (Pigment dispersion composition for a black matrix)

[0130] The resist composition for a black matrix of the present invention contains the pigment dispersion composition for a black matrix of the present invention described above.

[0131] As the content of the above pigment dispersion composition for a black matrix, based on the total mass of the resist composition for a black matrix of the present invention, it is preferably 30 to 80% by mass, more preferably 40 to 75% by mass.

[0132] (Photoinitiator)

[0133] The resist composition for a black matrix of the present invention preferably contains a photoinitiator.

[0134] As the above-mentioned photopolymerization initiator, there is no particular limitation as long as it is a polymerization initiator capable of generating free radicals and cations by irradiating active energy rays such as ultraviolet rays and electron beams. For example, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime)ethanone, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzoin dimethyl ether, α-hydroxyisobutylbenzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylbenzophenone, tert-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and other benzophenone-based, thioxanthone-based, anthraquinone-based, triazine-based photopolymerization initiators, etc.

[0135] The above-mentioned photopolymerization initiator can be used alone or in combination of two or more.

[0136] The content of the above-mentioned photopolymerization initiator, based on the mass fraction relative to the total solid content of the black matrix resist composition of the present invention, is preferably 1 to 20% by mass.

[0137] (Photopolymerizable compound)

[0138] The black matrix resist composition of the present invention preferably contains a photopolymerizable compound.

[0139] As the above-mentioned photopolymerizable compound, those compounds already described for the above-mentioned black matrix pigment dispersion composition can be appropriately selected and used.

[0140] The content of the above-mentioned photopolymerizable compound, based on the mass fraction relative to the total solid content of the black matrix resist composition of the present invention, is preferably 0.1 to 50% by mass.

[0141] (Alkali-soluble resin)

[0142] The black matrix resist composition of the present invention preferably contains an alkali-soluble resin.

[0143] As the above-mentioned alkali-soluble resin, a resin that preferably acts as a binder for the above-mentioned black dye and is soluble in the developer (especially an alkaline developer) used in the development treatment process when manufacturing the black matrix is preferred.

[0144] As the above alkali-soluble resin, a block copolymer may be used. By using a block copolymer, the dispersibility of the pigment can be improved compared with other copolymers, and solubility in PGMEA or an alkaline developer can be imparted.

[0145] Among these block copolymers, a block copolymer having a block composed of an ethylenically unsaturated monomer having one or more carboxyl groups and a block composed of other copolymerizable ethylenically unsaturated monomers is preferred.

[0146] As the above block copolymer, there is no particular limitation, and substances used in the past can be used. Specifically, examples include copolymers of ethylenically unsaturated monomers having a carboxyl group such as acrylic acid and methacrylic acid, and at least one ethylenically unsaturated monomer selected from the group consisting of 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 macromonomer, polymethyl methacrylate macromonomer, and carboxy epoxy diacrylate, and oligomers.

[0147] However, N-vinylpyrrolidone and monomers containing a sulfur element are preferably not used.

[0148] As the above block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used.

[0149] The block portion of a part of the above block copolymer may also be composed of a random copolymer.

[0150] As the above alkali-soluble resin, a cardo resin is preferred.

[0151] As the above cardo resin, those resins described in the above pigment dispersion composition for a black matrix can be appropriately used.

[0152] From the viewpoint of fine line adhesion, the acid value of the above alkali-soluble resin is preferably 5 to 300 mgKOH / g, more preferably 5 to 250 mgKOH / g, still more preferably 10 to 200 mgKOH / g, and particularly preferably 60 to 150 mgKOH / g.

[0153] From the viewpoints of fine line adhesion and solubility in an organic solvent, the weight average molecular weight of the above alkali-soluble resin is preferably 1000 to 100000, more preferably 1500 to 50000, still more preferably 2000 to 30000.

[0154] With respect to 100 parts by mass of the above-mentioned black dye, the content of the above-mentioned alkali-soluble resin is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass.

[0155] At this time, if the content of the above-mentioned alkali-soluble resin is less than 1 part by mass, the fine line adhesion may be reduced; if the content of the above-mentioned alkali-soluble resin exceeds 200 parts by mass, the concentration of the above-mentioned black dye is relatively reduced, and thus it may be difficult to achieve the target color concentration as a film.

[0156] As the above-mentioned alkali-soluble resin, it is preferably free of any of primary amino groups, secondary amino groups, and tertiary amino groups, and more preferably also free of quaternary ammonium groups. In addition, it is more preferably free of basic groups.

[0157] In addition, within the range that does not impair the effects of the present invention, an alkali-soluble resin having a structure other than a block copolymer may also be blended.

[0158] (Organic solvent)

[0159] As the above-mentioned organic solvent, an organic solvent described in the above-mentioned pigment dispersion composition for a black matrix can be appropriately selected and used.

[0160] As the content of the above-mentioned organic solvent, based on the total mass of the resist composition for a black matrix of the present invention, it is preferably 1 to 40% by mass, more preferably 5 to 35% by mass.

[0161] (Other additives)

[0162] The resist composition for a black matrix of the present invention can appropriately use various additives such as heat polymerization inhibitors, ultraviolet absorbers, antioxidants, and leveling agents as needed.

[0163] (Method for manufacturing a resist composition for a black matrix)

[0164] As a method for manufacturing the resist composition for a black matrix of the present invention, for example, preparing the pigment dispersion composition for a black matrix of the present invention, and then adding the remaining materials and stirring and mixing them using a stirring device or the like, thereby the resist composition for a black matrix of the present invention can be prepared.

[0165] As a method for performing the above-mentioned stirring and mixing, there is no particular limitation, and well-known methods such as an ultrasonic disperser, a high-pressure emulsifier, a bead mill, a three-roll mill, a sand mill, and a kneader can be used.

[0166] In addition, after the above-mentioned stirring and mixing, filtration can be performed using a filter.

[0167] <Black matrix>

[0168] The black matrix of the present invention is formed from the resist composition for black matrix of the present invention.

[0169] As a method for forming the black matrix of the present invention, there is no particular limitation. For example, the resist composition for black matrix of the present invention is coated on a transparent substrate, and after drying to form a coating film, a photomask is placed on the above coating film, image exposure and development are performed through the photomask, and if necessary, methods such as photocuring are used, whereby a black matrix can be formed.

[0170] For the method of coating, drying, exposing, and developing the resist composition for black matrix of the present invention, well-known methods can be appropriately selected.

[0171] In addition, as the above transparent substrate, well-known transparent substrates such as glass substrates and plastic substrates can be appropriately selected for use.

[0172] As the thickness of the above coating film, as the film thickness after drying, it is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and still more preferably 1 to 4 μm.

[0173] By setting it within the above thickness range, a specified pattern can be developed appropriately, and a specified optical density can be imparted appropriately.

[0174] The black matrix of the present invention has excellent fine line adhesion.

[0175] Specifically, if the fine line adhesion measured by the following method is 6 μm or less, it can be determined that the fine line adhesion is excellent.

[0176] The above fine line adhesion is measured by the following method.

[0177] The prepared resist composition for black matrix is coated on a glass substrate (Corning 1737, manufactured by Corning Inc.) using a spin coater so that the film thickness reaches 1 μm, and pre-baked at 100 °C for 2 minutes.

[0178] Next, a photomask having line patterns of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, and 30 μm is used, and exposure is performed using a high-pressure mercury lamp with a UV cumulative light amount of 80 mJ / cm 2 2.

[0179] Spray development is carried out in a 0.05% aqueous potassium hydroxide solution at 23 °C under 1.0 kgf / cm 2 2, and development is started from the time when the development pattern starts to appear (break time: conversion time), and development is ended at a time point that is 2 times the development start time (conversion time).

[0180] After the development is completed, spray water washing is carried out at a pressure of 1.0 kgf / cm 2 . The width (μm) of the smallest line pattern remaining on the glass substrate is evaluated.

[0181] The optical density (OD value) of the black matrix of the present invention is excellent.

[0182] Specifically, if the OD value is 2.80 or more, it can be judged that the optical density (OD value) is excellent.

[0183] The above OD value is preferably 2.85 or more, more preferably 2.90 or more.

[0184] The above optical density (OD value) is measured by the following method.

[0185] The produced black matrix resist composition is spin-coated on a glass substrate (Corning 1737, manufactured by Corning Incorporated) so that the film thickness reaches 1 μm, and pre-baked at 100 °C for 2 minutes.

[0186] Then, exposure is carried out with a high-pressure mercury lamp (UV cumulative light amount 80 mJ / cm 2 ), and then post-baked at 230 °C for 30 minutes and at 250 °C for 150 minutes to produce a black resist pattern (black matrix) formed only of solid portions.

[0187] The optical density of the produced black resist pattern (film thickness 1 μm) is measured using a transmission-type black densitometer (D200-II, manufactured by GretagMacbeth).

[0188] The black matrix of the present invention has a low reflectance (low Y value, low L * value).

[0189] If the above Y value is 5.80 or less and the above L * value is 29.00 or less, it can be judged that the reflectance is low enough.

[0190] The above Y value is preferably 5.80 or less, more preferably 5.70 or less.

[0191] In addition, the above L * value is preferably 29.00 or less, more preferably 28.50 or less.

[0192] The above Y value and L * value can be measured by the following method.

[0193] The produced black matrix resist composition was applied onto a glass substrate (Corning 1737, manufactured by Corning Incorporated) using a spin coater to achieve a film thickness of 1 μm, and pre-baked at 100 °C for 2 minutes to produce a coating film of only the solid part.

[0194] The L value of the glass surface was measured using a spectrophotometer (CM-26d, manufactured by Konica Minolta Inc.). * The Y value was calculated from the average value of the reflectance measurement values obtained under the condition of wavelengths from 360 to 740 nm.

[0195] The following technical solutions are disclosed in this specification.

[0196] The present disclosure (1) is a pigment dispersion composition for a black matrix, which comprises a pigment, a pigment dispersant, and a binder resin. The above pigment comprises a black pigment and a blue pigment. The above black pigment comprises carbon black, and the content of the above black pigment is 82% by mass or more and 95% by mass or less relative to the total mass of the above pigment.

[0197] The present disclosure (2) is the pigment dispersion composition for a black matrix according to the present disclosure (1), further comprising a pigment derivative, and the above pigment derivative is a sulfonated product of copper phthalocyanine.

[0198] The present disclosure (3) is the pigment dispersion composition for a black matrix according to the present disclosure (1) or (2), wherein the above blue pigment comprises at least one selected from C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 16, and C.I. Pigment Blue 60.

[0199] The present disclosure (4) is the pigment dispersion composition for a black matrix according to any one of the present disclosures (1) to (3), wherein the above black pigment contains acidic carbon black.

[0200] The present disclosure (5) is the pigment dispersion composition for a black matrix according to any one of the present disclosures (1) to (4), wherein the above binder resin is an alkali-soluble cardo resin.

[0201] The present disclosure (6) is a resist composition for a black matrix, which comprises the pigment dispersion composition for a black matrix according to any one of the present disclosures (1) to (5), a photopolymerizable compound, and a photoinitiator.

[0202] The present disclosure (7) is a black matrix, which is further formed from the resist composition for a black matrix according to the present disclosures (1) to (6).

[0203] Embodiment

[0204] Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited thereto without departing from its gist and application scope. It should be noted that in this embodiment, "parts" and "%" respectively represent "parts by mass" and "% by mass" unless otherwise specified.

[0205] The various materials used in the following examples and comparative examples are as described below.

[0206] <Black pigment>

[0207] Acidic carbon black (NEROX3500, average primary particle size of 31 nm, pH 2.5, product name: "NEROX3500", manufactured by Orion Engineered Carbons)

[0208] <Blue pigment>

[0209] C.I. Pigment Blue 15:6 (PB15:6)

[0210] C.I. Pigment Blue 15:3 (PB15:3)

[0211] C.I. Pigment Blue 15:4 (PB15:4)

[0212] C.I. Pigment Blue 16 (PB16)

[0213] C.I. Pigment Blue 60 (PB60)

[0214] <Pigment dispersant>

[0215] LPN6919 (a block copolymer composed of blocks having basic groups such as tertiary amino groups and quaternary ammonium bases and blocks having no functional groups, product name: "BYK-LPN6919", manufactured by BYK Chemie)

[0216] <Pigment derivative>

[0217] BYK2100 (sulfonated copper phthalocyanine, product name: "BYK-SYNERGIST2100", manufactured by BYK Chemie)

[0218] <Binder resin>

[0219] WR-301 (product name "WR-301", cardo resin, acid value 100 mgKOH / g, solid content 45% by mass, manufactured by ADEKA Corporation)

[0220] <Organic solvent>

[0221] PGMEA (propylene glycol monomethyl ether acetate)

[0222] <Photoinitiator>

[0223] OXE02 (Product name “Irgacure OXE02”, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime)ethanone, manufactured by BASF)

[0224] <Photopolymerizable compound>

[0225] DPHA (Dipentaerythritol hexaacrylate)

[0226] <Alkali-soluble resin>

[0227] WR-301 (Product name “WR-301”, Cardo resin, acid value 100 mgKOH / g, solid content 45 mass%, manufactured by ADEKA Corporation)

[0228] <Leveling agent>

[0229] Megafac F-554 (manufactured by DIC Corporation)

[0230] <Pigment dispersion composition for black matrix>

[0231] Mix each material to form the composition shown in Table 1, and knead with a bead mill for one day and night to prepare a pigment dispersion composition for black matrix.

[0232] [Table 1]

[0233]

[0234] <Resist composition for black matrix>

[0235] Using a high-speed mixer, the above pigment dispersion composition for black matrix was uniformly mixed with other materials (photoinitiator, photopolymerizable compound, alkali-soluble resin, and organic solvent) to achieve the composition shown in Table 2.

[0236] Thereafter, filtration was performed using a filter with a pore size of 3 μm to prepare resist compositions for black matrix for Examples and Comparative Examples.

[0237] In addition, in Table 2, the numerical values in the right column of each material of photoinitiator, photopolymerizable compound, alkali-soluble resin, and organic solvent represent the blending amounts.

[0238] <Evaluation test>

[0239] (Fine line adhesion)

[0240] The produced black matrix resist composition was applied onto a glass substrate (Corning 1737, manufactured by Corning Incorporated) using a spin coater to achieve a film thickness of 1 μm, and prebaked at 100 °C for 2 minutes.

[0241] Then, a photomask with line patterns of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, and 30 μm was used, and exposure was carried out using a high-pressure mercury lamp with a cumulative UV light amount of 80 mJ / cm 2 Exposure was performed.

[0242] In a 0.05% aqueous potassium hydroxide solution at 23 °C, under the condition of spray development at 1.0 kgf / cm 2 development was started from the time when the developed pattern started to appear (the conversion time), and development was ended at the time point that was 2 times the development start time (the conversion time).

[0243] After the development was completed, jet water washing was carried out at a pressure of 1.0 kgf / cm 2 The width (μm) of the smallest line pattern remaining on the above-mentioned glass substrate was evaluated. The results are shown in Table 2.

[0244] (Optical density)

[0245] The produced black matrix resist composition was applied onto a glass substrate (Corning 1737, manufactured by Corning Incorporated) using a spin coater to achieve a film thickness of 1 μm, and prebaked at 100 °C for 2 minutes.

[0246] Next, exposure was carried out using a high-pressure mercury lamp (cumulative UV light amount 80 mJ / cm 2 ), and post-baking was carried out at 230 °C for 30 minutes to produce a black resist pattern (black matrix) formed only by solid parts.

[0247] The optical density of the produced black resist pattern (film thickness 1 μm) was measured using a transmission-type black densitometer (D200-II, manufactured by GretagMacbeth). The results are shown in Table 2.

[0248] (Y value and L * value)

[0249] The produced black matrix resist composition was applied onto a glass substrate (Corning 1737, manufactured by Corning Incorporated) using a spin coater to achieve a film thickness of 1 μm, and a coating film with only solid parts was produced by prebaking at 100 °C for 2 minutes.

[0250] The L value of the glass surface was measured using a spectrocolorimeter (CM-26d, manufactured by Konica Minolta, Inc.), and the Y value was calculated from the average value of the reflectance measurement values obtained under the conditions of wavelengths from 360 to 740 nm. * The results are shown in Table 2.

[0251] The results are shown in Table 2.

[0252] [Table 2]

[0253]

[0254] It can be confirmed from Table 2 that in the examples using the pigment dispersion composition for a black matrix of the present invention, excellent fine line adhesion can be achieved when forming the black matrix, and a black matrix with excellent OD value (optical density) and low reflectance (low Y value, low L * value) can be formed.

[0255] Industrial Applicability

[0256] The pigment dispersion composition for a black matrix, the resist composition for a black matrix, and the black matrix of the present invention can preferably be used as a black matrix for an image display device, a touch panel, or the like.

Claims

1. A pigment dispersion composition for a black matrix, comprising a pigment, a pigment dispersant and a binder resin, wherein the pigment comprises a black pigment and a blue pigment, The black pigment comprises carbon black, The content of the black pigment is 82% by mass or more and 95% by mass or less relative to the total mass of the pigment.

2. The pigment dispersion composition for black matrix according to claim 1, wherein Also included is a pigment derivative, which is a sulfonate of copper phthalocyanine.

3. The pigment dispersion composition for black matrix according to claim 1 or 2, wherein The blue pigment includes at least one selected from CI Pigment Blue 15:6, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 16, and CI Pigment Blue 60.

4. The pigment dispersion composition for black matrix according to claim 1 or 2, wherein The black dye comprises acid carbon black.

5. The pigment dispersion composition for black matrix according to claim 1 or 2, wherein The binder resin is an alkali-soluble cardo resin. 6 . A resist composition for a black matrix, comprising the pigment dispersion composition for a black matrix according to claim 1 , a photopolymerizable compound, and a photopolymerization initiator. 7 . A black matrix formed using the resist composition for a black matrix according to claim 6 .

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