Pigment dispersion composition for display, pigment dispersion resist composition for display, and resist film

Abstract

To provide a pigment dispersion composition for display capable of forming a coating film having both solvent resistance to NMP and an excellent break point, and to provide a resist composition and a resist film.SOLUTION: A pigment dispersion composition for display includes a coloring pigment, a polymer pigment dispersant including a nitrogen atom-containing functional group, an alkali-soluble resin, and a solvent, in which the polymer pigment dispersant is any one of (I) to (III). (I) The nitrogen atom-containing functional group is a quaternary ammonium base. (II) The nitrogen atom-containing functional group contains 10% by mass or less of a tertiary amino group and 90% by mass or more of a quaternary ammonium base. (III) The ink composition contains first and second polymer pigment dispersants, the nitrogen atom-containing functional group of the first polymer pigment dispersant is a quaternary ammonium base, the nitrogen atom-containing functional group of the second polymer pigment dispersant is a tertiary amino group, and the content of the first polymer pigment dispersant is 50 mass% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a pigment dispersion composition for displays, a pigment dispersion resist composition for displays, and a resist film. More specifically, the present invention relates to a pigment dispersion composition for displays, a pigment dispersion resist composition for displays, and a resist film that can form a coating film that can achieve both solvent resistance to highly polar solvents such as N-methylpyrrolidone and an excellent break point. [Background technology]

[0002] Conventionally, black matrices, black photospacers, black column spacers, and pigment dispersion compositions for displays to form these have been developed to improve the quality, contrast, performance, etc. of liquid crystal displays. Patent Document 1 discloses a coloring composition that includes a dispersant containing a block copolymer having ACMO in the A block of the dispersant and constituted with acrylic acid, a colorant, a dispersion medium, and a binder resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-4308 Summary of the Invention [Problem to be solved by the invention]

[0004] The alignment film that constitutes a display is formed by applying a solution in which polyamic acid, a precursor of polyimide resin, is dissolved in a basic solvent with very high solubility, such as N-methylpyrrolidone (NMP). Therefore, parts that come into contact with the alignment film (such as black matrix, black photospacer, and black column spacer) are required to be resistant to highly polar solvents such as NMP. However, the coloring composition described in Patent Document 1 leaves room for improvement in terms of solvent resistance to solvents such as NMP. Furthermore, this coloring composition has problems such as its viscosity easily changing over time and its break point being poor.

[0005] The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a pigment dispersion composition for displays, a pigment dispersion resist composition for displays, and a resist film that are capable of forming a coating film that can achieve both solvent resistance to highly polar solvents such as N-methylpyrrolidone and an excellent break point. [Means for solving the problem]

[0006] The present inventors conducted extensive research to solve the above problems and discovered that the above problems can be solved simultaneously by combining a color pigment, a polymeric pigment dispersant having a nitrogen-containing functional group consisting of a specific quaternary ammonium salt group or tertiary ammonium salt group, a first alkali-soluble resin, and a solvent, thereby completing the present invention. The present invention, which solves the above problems, mainly comprises the following features.

[0007] (1) A pigment dispersion composition for displays, comprising a color pigment, a polymeric pigment dispersant containing a nitrogen atom-containing functional group, a first alkali-soluble resin, and a solvent, wherein the polymeric pigment dispersant is any one of the following (I) to (III): (I) The nitrogen atom-containing functional group of the polymeric pigment dispersant is a quaternary ammonium salt group. (II) The nitrogen atom-containing functional groups of the polymeric pigment dispersant contain 10% by mass or less of tertiary amino groups and 90% by mass or more of quaternary ammonium salt groups. (III) The polymeric pigment dispersant comprises a first polymeric pigment dispersant and a second polymeric pigment dispersant, the nitrogen atom-containing functional group of the first polymeric pigment dispersant is a quaternary ammonium salt group, the nitrogen atom-containing functional group of the second polymeric pigment dispersant is a tertiary amino group, and the content of the first polymeric pigment dispersant in the polymeric pigment dispersant is 50 mass% or more.

[0008] According to this configuration, the pigment dispersion composition for displays can form a coating film that can achieve both solvent resistance to highly polar solvents such as N-methylpyrrolidone and an excellent break point.

[0009] (2) The pigment dispersion composition for displays according to (1), wherein the color pigment comprises lactam black.

[0010] According to this configuration, the pigment-dispersed resist composition for displays can form a coating film with excellent solvent resistance against highly polar solvents such as N-methylpyrrolidone. Furthermore, the pigment-dispersed resist composition for displays has excellent development adhesion even when forming fine lines, allowing for the production of higher-definition displays. Furthermore, the resulting resist composition has a high OD value.

[0011] (3) A pigment dispersion resist composition for displays, comprising the pigment dispersion composition for displays according to (1) or (2), a second alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, wherein the second alkali-soluble resin comprises an alkali-soluble resin having a crosslinkable functional group.

[0012] According to this configuration, the pigment-dispersed resist composition for displays can form a coating film having excellent solvent resistance against highly polar solvents such as N-methylpyrrolidone. Furthermore, the pigment-dispersed resist composition for displays has excellent development adhesion even when forming fine lines, and can produce a high-definition display.

[0013] (4) A resist film formed from the pigment-dispersed resist composition for displays according to (3).

[0014] According to this configuration, the resist film has superior solvent resistance to highly polar solvents such as N-methylpyrrolidone. Furthermore, the resist film has excellent development adhesion even when fine lines are formed, making it possible to obtain a high-definition display. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a pigment dispersion composition for displays, a pigment dispersion resist composition for displays, and a resist film that are capable of forming a coating film that can achieve both solvent resistance to highly polar solvents such as N-methylpyrrolidone and an excellent break point. DETAILED DESCRIPTION OF THE INVENTION

[0016] <Pigment dispersion composition for displays> A pigment dispersion composition for displays (hereinafter also referred to as a pigment dispersion composition) according to one embodiment of the present invention comprises a color pigment, a polymeric pigment dispersant containing a nitrogen atom-containing functional group, a first alkali-soluble resin, and a solvent. The polymeric pigment dispersant is any one of the following (I) to (III). Each of these will be described below. (I) The nitrogen atom-containing functional group of the polymeric pigment dispersant is a quaternary ammonium salt group. (II) The nitrogen atom-containing functional groups of the polymeric pigment dispersant contain 10% by mass or less of tertiary amino groups and 90% by mass or more of quaternary ammonium salt groups. (III) The polymeric pigment dispersant comprises a first polymeric pigment dispersant and a second polymeric pigment dispersant, the nitrogen atom-containing functional group of the first polymeric pigment dispersant is a quaternary ammonium salt group, the nitrogen atom-containing functional group of the second polymeric pigment dispersant is a tertiary amino group, and the content of the first polymeric pigment dispersant in the polymeric pigment dispersant is 50 mass% or more.

[0017] (color pigments) The color pigment is not particularly limited, and is, for example, at least one selected from organic pigments and black pigments.

[0018] Examples of organic pigments include dye lake pigments, azo-based, benzimidazolone-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo-based, thioindigo-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, isoindolinone-based, nitro-based, nitroso-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, and indanthrone-based pigments. Examples of inorganic pigments include carbon black, titanium oxide, red iron oxide, graphite, iron black, chromium oxide green, and aluminum hydroxide.

[0019] More specifically, yellow pigments include CI Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, 213, and the like.

[0020] Magenta pigments include CI Pigment Red 5, 7, 12, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57, 57:1, 63:1, 101, 102, 112, 122, 123, 144, 146, 149, 168, 177, 178, 179, 180, 184, 185, 190, 202, 209, 224, 242, 254, 255, and 270, and CI Pigment Violet 19, 23, 29, 32, and 37.

[0021] Cyan pigments include CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 22, 27, 29, 6, etc.

[0022] Green pigments include CI Pigment Green 7, 8, 26, 36, 50, 58, 59, etc.

[0023] The black pigment is lactam black, carbon black (CI Pigment Black 7), etc. In this embodiment, the following lactam black is preferred.

[0024] Lactam Black The lactam black may be any known lactam black. For example, the lactam black of this embodiment has the following main skeleton, and more specifically, is Irgaphor Black S 0100 CF (manufactured by DIC Corporation). When the lactam black has the following main skeleton, hydrogen atoms in the main skeleton may be appropriately substituted with low-molecular-weight functional groups (for example, hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups; acidic groups such as carboxyl groups, sulfonic acid groups, and phosphonic acid groups; basic groups such as amino groups; hydroxyl groups; etc.) or halogen atoms.

[0025] [ka]

[0026] The volume-based particle size D50 of the lactam black of this embodiment is preferably 70 nm or more, more preferably 85 nm or more. Furthermore, the D50 value is preferably 130 nm or less, more preferably 115 nm or less. By having a D50 value within the above range, the pigment in the resulting pigment dispersion composition is less likely to settle and has good viscosity stability. Furthermore, the pigment dispersion composition provides a resist film with good linearity and roughness.

[0027] The volume-based particle size D90 of lactam black is preferably 160 nm or more, more preferably 180 nm or more. Furthermore, the D90 value is preferably 300 nm or less, more preferably 280 nm or less. By having the D90 value within the above range, the pigment in the resulting pigment dispersion composition is less likely to settle and has good viscosity stability. Furthermore, the resulting pigment dispersion composition provides a resist film with good linearity and roughness.

[0028] In this embodiment, the volume-based particle size can be measured by a laser diffraction particle size measurement method using Nanotrac (UPA-EX150, manufactured by Nikkiso Co., Ltd.).

[0029] The content of the color pigment is not particularly limited. For example, the content of the color pigment in the pigment dispersion composition is preferably 3% by mass or more, more preferably 5% by mass or more. Furthermore, the content of the color pigment in the pigment dispersion composition is preferably 25% by mass or less, more preferably 20% by mass or less. When the content of the color pigment is within the above range, the pigment dispersion composition provides a resist film with good OD value and development adhesion.

[0030] (Acidic group-containing pigment dispersing aid) The pigment dispersion composition of this embodiment may contain an acidic group-containing pigment dispersing aid to further improve pigment dispersibility. The acidic group-containing pigment dispersing aid is not particularly limited. Examples of acidic group-containing pigment dispersing aids include lactam black, perylene compounds, diketopyrrolopyrrole compounds, naphthol azo compounds, dioxazine compounds, quinacridone compounds, phthalocyanine compounds and their metal complexes, anthraquinone, naphthalene, acridone, or triazine pigments, into which an acidic group such as a carboxyl group or a sulfonic acid group has been introduced (acidic group-containing pigment derivatives), and compounds obtained by neutralizing these with an organic amine or the like. The acidic group-containing pigment derivative is preferably a phthalocyanine-based (having a phthalocyanine skeleton) pigment derivative having a sulfonic acid group or a naphthol azo pigment derivative having a sulfonic acid group, because they provide good dispersibility for colored pigments.

[0031] The content of the acidic group-containing pigment dispersing aid is not particularly limited. For example, the content of the acidic group-containing pigment dispersing aid is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the color pigment. Furthermore, the content of the acidic group-containing pigment dispersing aid is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, relative to 100 parts by mass of the color pigment.

[0032] (Polymer pigment dispersant containing nitrogen atom-containing functional group) The polymeric pigment dispersant containing a nitrogen atom-containing functional group (hereinafter also referred to as polymeric pigment dispersant) of this embodiment is any one of the following (I) to (III). (I) The nitrogen atom-containing functional group of the polymeric pigment dispersant is a quaternary ammonium salt group. (II) The nitrogen atom-containing functional groups of the polymeric pigment dispersant contain 10% by mass or less of tertiary amino groups and 90% by mass or more of quaternary ammonium salt groups. (III) The polymeric pigment dispersant comprises a first polymeric pigment dispersant and a second polymeric pigment dispersant, the nitrogen atom-containing functional group of the first polymeric pigment dispersant is a quaternary ammonium salt group, the nitrogen atom-containing functional group of the second polymeric pigment dispersant is a tertiary amino group, and the content of the first polymeric pigment dispersant in the polymeric pigment dispersant is 50 mass% or more.

[0033] Polymeric pigment dispersants related to (I) The nitrogen atom-containing functional group of the polymeric pigment dispersant (I) is a quaternary ammonium base. Examples of the polymeric pigment dispersant (I) include polymethyl methacrylate-based quaternary ammonium base dispersants, polyacrylic acid-based quaternary ammonium base dispersants, polyoxyethylene-based quaternary ammonium base dispersants, and block copolymer-based quaternary ammonium base dispersants.

[0034] The polymethyl methacrylate-based quaternary ammonium base dispersant is a polymer compound in which a quaternary ammonium group is introduced into the PMMA skeleton. The polymethyl methacrylate-based quaternary ammonium base dispersant is not particularly limited. Examples of the polymethyl methacrylate-based quaternary ammonium base dispersant include polymethyl methacrylate-co-methacryloyloxyethyl trimethyl ammonium chloride (PMMA-co-METAC), polymethyl methacrylate-co-dimethylaminoethyl methacrylate (PMMA-co-DMAEMA), polymethyl methacrylate-co-benzyl trimethyl ammonium chloride (PMMA-co-BTMA), polymethyl methacrylate-co-methyl methacrylate trimethyl ammonium chloride (PMMA-co-MTMAC), polymethyl methacrylate-co-methacryloyloxypropyl trimethyl ammonium chloride (PMMA-co-MAPTAC), poly(methyl methacrylate)-co-(dimethylaminoethyl methacrylate)-co-(benzyl chloride) (PMMA-co-DMAEMA-Bz). Cl), poly(methyl methacrylate)-co-(methacryloyloxyethyltrimethylammonium chloride)-co-(benzyl chloride) (PMMA-co-METAC-BzCl), poly(methyl methacrylate)-co-(benzyltrimethylammonium chloride)-co-(benzyl chloride) (PMMA-co-BTMA-BzCl), poly(methyl methacrylate)-co-(methyl methacrylate trimethylammonium chloride)-co-(benzyl chloride) (PMMA-co-MTMAC-BzCl), poly(methyl methacrylate)-co-(methacryloyloxypropyltrimethylammonium chloride)-co-(benzyl chloride) (PMMA-co-MAPTAC-BzCl), poly(methyl methacrylate)-co-(betaine methacrylate)-co-(benzyl chloride) (PMMA-co-MAB-BzCl), etc.

[0035] The polyacrylic acid-based quaternary ammonium base dispersant is a polymer compound in which a quaternary ammonium group is introduced into the polyacrylic acid skeleton. The polyacrylic acid-based quaternary ammonium base dispersant is not particularly limited. Examples of the polyacrylic acid-based quaternary ammonium base dispersant include polyacrylic acid-co-dimethylaminoethyl methacrylate (PAA-co-DMAEMA), polyacrylic acid-co-methacryloyloxyethyl trimethyl ammonium chloride (PAA-co-METAC), polyacrylic acid-co-benzyl trimethyl ammonium chloride (PAA-co-BTMA), polyacrylic acid-co-methyl methacrylate trimethyl ammonium chloride (PAA-co-MTMAC), polyacrylic acid-co-methacryloyloxypropyl trimethyl ammonium chloride (PAA-co-MAPTAC), polyacrylic acid-co-betaine methacrylate (PAA-co-MAB), polyacrylic acid-co-(dimethylaminoethyl methacrylate)-co-(benzyl chloride) ( Examples include polyacrylic acid-co-(methacryloyloxyethyltrimethylammonium chloride)-co-(benzyl chloride) (PAA-co-METAC-BzCl), polyacrylic acid-co-(benzyltrimethylammonium chloride)-co-(benzyl chloride) (PAA-co-BTMA-BzCl), polyacrylic acid-co-(methyltrimethylammonium chloride)-co-(benzyl chloride) (PAA-co-MTMAC-BzCl), polyacrylic acid-co-(methacryloyloxypropyltrimethylammonium chloride)-co-(benzyl chloride) (PAA-co-MAPTAC-BzCl), and polyacrylic acid-co-(betaine methacrylate)-co-(benzyl chloride) (PAA-co-MAB-BzCl).

[0036] The polyoxyethylene-based quaternary ammonium base dispersant is a polymer compound in which a quaternary ammonium group is introduced into the polyoxyethylene skeleton. The polyoxyethylene-based quaternary ammonium base dispersant is not particularly limited. Examples of the polyoxyethylene-based quaternary ammonium base dispersant include polyethylene glycol-block-dimethylaminoethyl methacrylate (PEG-b-DMAEMA), polyethylene glycol-block-methacryloyloxyethyl trimethyl ammonium chloride (PEG-b-METAC), polyethylene glycol-block-benzyl trimethyl ammonium chloride (PEG-b-BTMA), polyethylene glycol-block-methyl methacrylate trimethyl ammonium chloride (PEG-b-MTMAC), polyethylene glycol-block-methacryloyloxypropyl trimethyl ammonium chloride (PEG-b-MAPTAC), polyethylene glycol-block-betaine methacrylate (PEG-b-MAB), polyoxyethylene-co-(dimethylaminoethyl methacrylate)- co-(benzyl chloride) (POE-co-DMAEMA-BzCl), polyoxyethylene-co-(methacryloyloxyethyltrimethylammonium chloride)-co-(benzyl chloride) (POE-co-METAC-BzCl), polyoxyethylene-co-(benzyltrimethylammonium chloride)-co-(benzyl chloride) (POE-co-BTMA-BzCl), polyoxyethylene-co-(methyl methacrylate trimethylammonium chloride)-co-(benzyl chloride) (POE-co-MTMAC-BzCl), polyoxyethylene-co-(methacryloyloxypropyltrimethylammonium chloride)-co-(benzyl chloride) (POE-co-MAPTAC-BzCl), polyoxyethylene-co-(betaine methacrylate)-co-(benzyl chloride) (POE-co-MAB-BzCl), and the like.

[0037] The block copolymer-based quaternary ammonium base dispersant is not particularly limited. Examples of the block copolymer-based quaternary ammonium base dispersant include poly(ethylene oxide)-block-poly(dimethylaminoethyl methacrylate) (PEO-b-PDMAEMA), poly(ethylene oxide)-block-poly(methacryloyloxyethyltrimethylammonium chloride) (PEO-b-PMETAC), poly(ethylene oxide)-block-poly(benzyltrimethylammonium chloride) (PEO-b-PBTMA), and poly(ethylene oxide)-block-poly(methyl methacrylate). Poly(ethylene oxide)-block-poly(methacryloyloxypropyltrimethylammonium chloride) (PEO-b-PMTMAC), poly(ethylene oxide)-block-poly(methacryloyloxypropyltrimethylammonium chloride) (PEO-b-PMAPTAC), poly(ethylene oxide)-block-poly(methacrylic acid betaine) (PEO-b-PMAB), poly(propylene oxide)-block-poly(dimethylaminoethyl methacrylate) (PPO-b-PDMAEMA), polyethylene glycol-block-poly(dimethylaminoethyl methacrylate) Poly(methacryloyloxyethyltrimethylammonium chloride-co-benzyl chloride) (PEG-b-PDMAEMA-BzCl), polyethylene glycol-block-poly(methacryloyloxyethyltrimethylammonium chloride-co-benzyl chloride) (PEG-b-PMETAC-BzCl), polyethylene glycol-block-poly(benzyltrimethylammonium chloride-co-benzyl chloride) (PEG-b-PBTMA-BzCl), polyethylene glycol-block-poly(methyl methacrylate trimethylammonium chloride-co-benzyl chloride) ) (PEG-b-PMTMAC-BzCl), polyethylene glycol-block-poly(methacryloyloxypropyltrimethylammonium chloride-co-benzyl chloride) (PEG-b-PMAPTAC-BzCl), polyethylene glycol-block-poly(betaine methacrylate-co-benzyl chloride) (PEG-b-PMAB-BzCl), poly(propylene oxide)-block-poly(dimethylaminoethyl methacrylate-co-benzyl chloride) (PPO-b-PDMAEMA-BzCl), etc.

[0038] A commercially available product of the pigment dispersion composition (I) is LPN21324 (manufactured by BYK-Chemie Co., Ltd.).

[0039] The weight-average molecular weight of the polymeric pigment dispersant (I), measured by GPC in terms of polystyrene, is preferably at least 3,000, and more preferably at least 5,000. The weight-average molecular weight of the polymeric pigment dispersant (I) is preferably at most 100,000, and more preferably at most 50,000. When the weight-average molecular weight is within the above range, the pigment dispersion composition (I) has excellent viscosity stability.

[0040] (II) Polymeric pigment dispersants The polymeric pigment dispersant (II) has a nitrogen atom-containing functional group containing a quaternary ammonium salt group and a tertiary amino group. More specifically, the polymeric pigment dispersant (II) is a polymeric pigment dispersant containing a quaternary ammonium salt group and a tertiary amino group. More specifically, the polymeric pigment dispersant (II) is a polymeric pigment dispersant containing a quaternary ammonium salt group and a tertiary amino group. More specifically, the polymeric pigment dispersant (II) is a polymeric pigment dispersant containing a quaternary ammonium salt group and a tertiary amino group. More specifically, the polymeric pigment dispersant (II) is a polymeric pigment dispersant containing a quaternary ammonium salt group and a tertiary amino group. poly(vinylpyrrolidone-co-acrylamide-co-dimethylaminoethyl methacrylate-co-benzyltrimethylammonium chloride) (PVP-co-AAm-co-DMAEMA-co-BTAC), poly(acrylic acid-co-dimethylaminoethyl methacrylate-co-methacryloyloxypropyltrimethylammonium chloride) (PAA-co-DMAEMA-co-MAPTAC), etc.

[0041] Here, (II) is distinguished from (I) in that it specifies that the tertiary amino group is contained in an amount of 10 mass% or less, rather than 100 mass% of the quaternary ammonium salt group. That is, in (II), the tertiary amino group is contained in an amount exceeding 0 mass% and 10 mass% or less in the structure of the polymer pigment dispersant.

[0042] In the structure of the polymeric pigment dispersant (II), the quaternary ammonium salt group may be 90% by mass or more. Alternatively, the quaternary ammonium salt group may be 100% by mass. This provides the pigment dispersion composition with superior solvent resistance to highly polar solvents such as N-methylpyrrolidone.

[0043] The amine value of the polymeric pigment dispersant (II) is preferably 60 mgKOH / g or less, and more preferably 40 mgKOH / g or less. When the amine value is within the above range, the pigment dispersion composition (II) has better viscosity stability. In this embodiment, the amine value indicates the total amount of free base and base, and is a value expressed in mg of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize 1 g of sample.

[0044] The weight-average molecular weight of the polymeric pigment dispersant (II), measured by GPC in terms of polystyrene, is preferably at least 3,000, and more preferably at least 5,000. The weight-average molecular weight of the polymeric pigment dispersant (II) is preferably at most 100,000, and more preferably at most 50,000. When the weight-average molecular weight is within the above range, the pigment dispersion composition (II) has excellent viscosity stability.

[0045] (III) Polymeric pigment dispersants The polymeric pigment dispersant (III) includes a first polymeric pigment dispersant and a second polymeric pigment dispersant.

[0046] The nitrogen atom-containing functional group of the first polymeric pigment dispersant is a quaternary ammonium salt group. Such a first polymeric pigment dispersant is the same as the polymeric pigment dispersant described above in "Polymeric pigment dispersant related to (I)."

[0047] The nitrogen atom-containing functional group of the second polymeric pigment dispersant is a tertiary amino group. There are no particular limitations on the type of second polymeric pigment dispersant. Examples of the second polymeric pigment dispersant include polymethyl methacrylate-co-dimethylaminoethyl methacrylate (PMMA-co-DMAEMA), polyacrylamide-co-dimethylaminoethyl methacrylate (PAAm-co-DMAEMA), polyvinylpyrrolidone-co-dimethylaminoethyl methacrylate (PVP-co-DMAEMA), poly(MMA-co-BMA-co-DMAEMA), poly(BMA-co-MMA-co-DMAEMA-co-MPEG13A), and poly(DMAEMA-co-MMA-co-BMA-co-MPEG13A).

[0048] In the polymeric pigment dispersant (III), the first polymeric pigment dispersant may account for 50% by mass or more, and preferably 70% by mass or more, of the polymeric pigment dispersant, which provides the pigment dispersion composition with superior solvent resistance to highly polar solvents such as N-methylpyrrolidone.

[0049] Returning to the explanation of the polymeric pigment dispersant as a whole, the content of the polymeric pigment dispersant is not particularly limited. For example, the content of the polymeric pigment dispersant in the pigment dispersion composition is preferably 1.0% by mass or more, and more preferably 3.0% by mass or more. Furthermore, the content of the polymeric pigment dispersant in the pigment dispersion composition is preferably 8.0% by mass or less, and more preferably 6.0% by mass or less. By having the content of the polymeric pigment dispersant within the above range, the pigment dispersion composition has excellent viscosity stability and solvent resistance.

[0050] (First alkali-soluble resin) The first alkali-soluble resin is blended, for example, to prepare a partition pattern of a color filter (e.g., a partition pattern in black matrix applications), and also to prepare a partition pattern of a color filter and spacers of a liquid crystal layer (e.g., spacers in black photospacer and black column spacer applications).

[0051] The first alkali-soluble resin is not particularly limited. Examples include acrylic copolymer resins, maleic acid copolymer resins, polyester resins obtained by condensation polymerization, epoxy acrylate resins obtained by addition polymerization of acrylic acid and an epoxy compound, and urethane acrylate resins obtained by polymerization of acrylic acid, a polyol, and an isocyanate compound. This makes it easier to obtain a high-resolution display using the pigment dispersion composition. Among these, the first alkali-soluble resin is preferably an acrylic copolymer resin or an epoxy acrylate resin because of its excellent developability and development adhesion.

[0052] The first alkali-soluble resin is not particularly limited. For example, the first alkali-soluble resin is a resin containing an anionic group such as a carboxyl group, a sulfonic acid group, or a phosphonic acid group (-P(=O)(OH)).

[0053] The acrylic resin is not particularly limited, and examples thereof include the "Pholette" series manufactured by Soken Chemical & Engineering Co., Ltd., such as ZAH-106, ZAH-110, ZAH-115, and ZAH-310.

[0054] The epoxy acrylate resin is not particularly limited. Examples of the epoxy acrylate resin include the "KAYARAD" series manufactured by Nippon Kayaku Co., Ltd., CCR-1291H, CCR-1235, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, ZCR-1601H, ZCR-1797H, ZCR-1798H, UXE-3000, and UXE-3024.

[0055] The urethane acrylate resin is not particularly limited, and examples thereof include the "KAYARAD" series manufactured by Nippon Kayaku Co., Ltd., such as UX-3204, UX-4101, UXT-6100, UX-8101, UX-0937, DPHA-40H, and UX-5000.

[0056] From the viewpoint of alkali developability, the acid value of the first alkali-soluble resin is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. The acid value is preferably 300 mgKOH / g or less, more preferably 200 mgKOH / g or less. In this embodiment, the acid value is measured according to JIS K 5601-2-1:1999.

[0057] The weight-average molecular weight of the first alkali-soluble resin is preferably 1,000 or more, more preferably 3,000 or more, from the viewpoint of film-forming properties such as resist films. Furthermore, the weight-average molecular weight of the alkali-soluble resin is preferably 100,000 or less, more preferably 50,000 or less, from the viewpoint of improving solubility. The weight-average molecular weight can be measured by gel permeation chromatography (GPC). For example, chromatography can be performed using a Water 2690 (manufactured by Waters) GPC apparatus and a PLgel 5μ MIXED-D (manufactured by Polymer Laboratories) column under the following conditions: tetrahydrofuran as the developing solvent, a column temperature of 25°C, a flow rate of 1 milliliter / minute, an RI detector, a sample injection concentration of 10 milligrams / milliliter, and an injection volume of 100 microliters, and the weight-average molecular weight can be calculated as polystyrene equivalent.

[0058] The content of the first alkali-soluble resin is not particularly limited. For example, the content of the first alkali-soluble resin is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the color pigment. Furthermore, the content of the first alkali-soluble resin is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less, per 100 parts by mass of the color pigment. When the content of the first alkali-soluble resin is within the above range, the pigment dispersion composition is likely to produce a high-definition display.

[0059] (solvent) The pigment dispersion composition of the present embodiment contains a solvent. The solvent is not particularly limited. For example, from the viewpoint of stably dispersing the color pigment and sufficiently dissolving the first alkali-soluble resin and the like, the solvent is preferably an ester-based solvent, an ether-based solvent, an ether ester-based solvent, a ketone-based solvent, an aromatic hydrocarbon-based solvent, or a nitrogen-containing solvent.

[0060] Examples of ester solvents include 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, hydroxyacetic acid esters, and n-amyl formate.

[0061] Examples of the ether solvent include 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.

[0062] Examples of the ether ester solvent include 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.

[0063] The ketone solvents include methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone.

[0064] The aromatic hydrocarbon solvents include toluene, xylene, and alkylnaphthalene.

[0065] The nitrogen-containing solvents include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0066] The content of the solvent is not particularly limited. For example, the content of the solvent in the pigment dispersion composition is preferably 40% by mass or more, and more preferably 50% by mass or more. Furthermore, the content of the solvent in the pigment dispersion composition is preferably 90% by mass or less, and more preferably 80% by mass or less. When the content of the solvent is within the above range, the pigment dispersion composition has excellent dispersion stability of the colored pigment.

[0067] Returning to the description of the pigment dispersion composition as a whole, the method for preparing the pigment dispersion composition of the present embodiment is not particularly limited. For example, the pigment dispersion composition can be prepared by mixing various materials and kneading the mixture overnight using a bead mill or the like.

[0068] As described above, the pigment dispersion composition of this embodiment has excellent viscosity stability and can form a coating film that has excellent solvent resistance to highly polar solvents such as N-methylpyrrolidone. Therefore, the pigment dispersion composition is suitable for displays, and is particularly suitable for black matrices, black photospacers, black column spacers, and the like. Specifically, when the pigment dispersion composition of this embodiment is used for black matrices, black photospacers, or black column spacers, the display is less likely to malfunction and is less susceptible to deterioration.

[0069] <Pigment-dispersed resist composition for displays> A pigment dispersion resist composition for displays (hereinafter also referred to as a resist composition) according to one embodiment of the present invention comprises the above-described pigment dispersion composition for displays, a second alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator. The second alkali-soluble resin comprises an alkali-soluble resin having a crosslinkable functional group. The second alkali-soluble resin may be the same as the first alkali-soluble resin. Each of these will be described below.

[0070] (Pigment dispersion composition for displays) The pigment dispersion composition for displays (hereinafter also referred to as the pigment dispersion composition) is as described above, and therefore the description will be omitted where appropriate.

[0071] The content of the pigment dispersion composition is not particularly limited. For example, the content of the pigment dispersion composition is preferably 20% by mass or more, and more preferably 30% by mass or more. Furthermore, the content of the pigment dispersion composition is preferably 60% by mass or less, and more preferably 50% by mass or less. When the content of the pigment dispersion composition is within the above range, the resist composition is likely to achieve both development adhesion and an OD value.

[0072] (First alkali-soluble resin) The first alkali-soluble resin is the same as described above, and therefore a description thereof will be omitted.

[0073] (Second alkali-soluble resin) The second alkali-soluble resin is blended to improve the developability with an alkaline developer and the solvent resistance. There are no particular limitations on the second alkali-soluble resin, as long as it is an alkali-soluble resin having a crosslinking functional group. For example, the second alkali-soluble resin is an alkali-soluble resin having a crosslinking functional group among the first alkali-soluble resins described above in relation to the pigment dispersion composition. Specifically, the second alkali-soluble resin is preferably an epoxy acrylate resin, an epoxy resin, an acrylic resin, or a urethane resin, and more preferably an epoxy acrylate resin.

[0074] The content of the second alkali-soluble resin is not particularly limited. For example, the content of the second alkali-soluble resin in the resist composition is preferably 3% by mass or more, and more preferably 5% by mass or more. Furthermore, the content of the second alkali-soluble resin in the resist composition is preferably 15% by mass or less, and more preferably 12% by mass or less. By keeping the content of the second alkali-soluble resin within the above range, the resist composition has an appropriate range of developability with an alkaline developer.

[0075] (Photopolymerizable compound) The photopolymerizable compound is not particularly limited, and examples thereof include monomers and oligomers having a photopolymerizable unsaturated bond.

[0076] Examples of the monomer having one photopolymerizable unsaturated bond include alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; aralkyl methacrylates or acrylates such as benzyl methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyethyl methacrylate and butoxyethyl acrylate; and aminoalkyl methacrylates such as N,N-dimethylaminoethyl methacrylate and N,N-dimethylaminoethyl acrylate. Methacrylates or acrylates; methacrylic acid esters or acrylic acid esters of polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.; methacrylic acid esters or acrylic acid esters 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.

[0077] Monomers having two or more photopolymerizable unsaturated bonds include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol 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, and dipentaerythritol tetramethacrylate. Examples of such acrylates include erythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol 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 hexaacrylate, and dipentaerythritol pentaacrylate.

[0078] The oligomer having a photopolymerizable unsaturated bond is obtained by appropriately polymerizing the above-mentioned monomers, for example.

[0079] The content of the photopolymerizable compound is not particularly limited. For example, the content of the photopolymerizable compound in the resist composition is preferably 1% by mass or more, and more preferably 2.5% by mass or more. Furthermore, the content of the photopolymerizable compound in the resist composition is preferably 15% by mass or less, and more preferably 10% by mass or less. By having the content of the photopolymerizable compound within the above range, the resist composition is likely to achieve both curability and alkaline developability of the resist film.

[0080] (Photopolymerization initiator) The photopolymerization initiator is not particularly limited. Examples of the photopolymerization initiator include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzil, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzil dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, triazine-based photopolymerization initiators, and oxime ester-based photopolymerization initiators.

[0081] The content of the photopolymerization initiator is not particularly limited. For example, the content of the photopolymerization initiator in the resist composition is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more. Furthermore, the content of the photopolymerization initiator in the resist composition is preferably 5% by mass or less, and more preferably 2% by mass or less. By keeping the content of the photopolymerization initiator within the above range, the resist composition is likely to achieve both the curability and fine line adhesion of the resist film.

[0082] Furthermore, additives such as a leveling agent, an antioxidant, and an antifoaming agent may be added to the resist composition as needed.

[0083] There are no particular limitations on the method for preparing the resist composition of this embodiment. As an example, the resist composition can be prepared by co-dispersing various materials using a stirrer or the like.

[0084] The resist composition of this embodiment has excellent viscosity stability. Furthermore, the resist composition can suppress a decrease in OD value (optical density) during the waiting time between resist application to a substrate and pre-baking. The resulting resist film has low reflectance and excellent development adhesion, allowing for the production of high-definition displays.

[0085] <Resist film> A resist film according to one embodiment of the present invention is a resist film formed from the above-described pigment-dispersed resist composition for displays.

[0086] The method for forming the resist film is not particularly limited. For example, the resist film can be obtained by a known means using the above-mentioned pigment-dispersed resist composition for displays. Specifically, the resist film can be obtained by applying the above-mentioned resist composition to a transparent substrate, drying it to form a coating film, placing a photomask on the coating film, and forming a colored matrix (for example, a black matrix) by a method such as image exposure through the photomask, development, and, if necessary, photocuring.

[0087] The substrate is not particularly limited, and examples thereof include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, and an array substrate.

[0088] The methods for applying, drying, exposing, and developing the resist composition can be appropriately selected from known methods.

[0089] Examples of methods for applying the resist composition include screen printing, roll coating, curtain coating, spray coating, and spin coating. After applying the resist composition, the applied layer may be heated, if necessary, using a heating means such as a circulation oven, an infrared heater, or a hot plate to volatilize the solvent contained in the resin layer. Heating conditions may be appropriately set depending on the composition of the resist composition used. Generally, heating conditions are a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0090] The thickness of the coating film (after drying) is not particularly limited. For example, the thickness of the coating film is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm. When the thickness of the coating film is within the above range, the obtained colored matrix is ​​likely to be favorably developed into a predetermined pattern and to exhibit a predetermined optical density.

[0091] The exposure method is not particularly limited. For example, the exposure method is irradiation with active energy rays such as ultraviolet rays and excimer laser light. The amount of energy radiation may be appropriately set depending on the composition of the resist composition. For example, the energy dye may be irradiated with an amount of 30 to 2000 mJ / cm. 2 The light source used for exposure is not particularly limited. Examples of the light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp.

[0092] The alkaline developer used for development is not particularly limited. Examples of the developer include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; and aqueous solutions of p-phenylenediamine compounds such as tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, and 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates thereof. The alkaline developer may contain, as needed, an antifoaming agent, a surfactant, or the like.

[0093] After the alkali development, the resin can be hardened by post-baking. The post-baking conditions are not particularly limited. For example, the post-baking conditions are a temperature of 80°C to 250°C and a time of 10 minutes to 4 hours.

[0094] As described above, the resist film of this embodiment is obtained using a resist composition containing the pigment dispersion composition described above. Therefore, the resist film has superior solvent resistance to highly polar solvents such as N-methylpyrrolidone. Furthermore, the resist film has excellent development adhesion even when fine lines are formed, allowing for the production of high-definition displays. Therefore, the resist film is suitable for use in image display devices, touch panels, and the like that use high-definition displays. [Example]

[0095] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

[0096] The raw materials used are shown below. In the following, the abbreviations are as follows: MMA: methyl methacrylate BMA: butyl methacrylate MPEG13A:CH2=CHCOO(C2H4O) 13 CH3 DMAEMA: Dimethylaminoethyl methacrylate DMAEMA·BzCl: DMAEMA benzyl chloride quaternary salt DMAPAA: dimethylaminopropylacrylamide DMAPAA·BzCl: Quaternary benzyl chloride of DMAPAA BzCl: benzyl chloride MeOH: Methanol

[0097] Regarding the composition of the pigment dispersants, the parts in parentheses in the composition column indicate blocks, and the numbers separated by " / " indicate the mass ratio of each monomer. " / / " indicates the mass ratio of each block. All dispersants are in the form of a solution, dissolved in a mixed solvent with a composition and mixing ratio of PGMEA:PGME = 2:1, to a solids concentration of 40 mass%. " / / " in the composition column indicates that the blocks consisting of the monomers in parentheses on both sides are block copolymerized. If not enclosed in parentheses, it is a random polymer. For example, the following polymeric pigment dispersant 4-1 indicates a block copolymer of a randomly polymerized block of MMA and BMA and a block polymerized DMAEMA, which are then quaternized with benzyl chloride (BzCl). The numerical values ​​in the composition indicate that, as described in the section on the preparation of the solution of polymeric pigment dispersant 4-1, the total mass of this block copolymer is 34.4 parts by mass of MMA, 34.4 parts by mass of BMA, and 31.2 parts by mass of DMAEMA·BzCl.

[0098] <Coloring pigments> Irgaphor BLACK: S0100CF: DIC Corporation, Lactam Black Paliotol Yellow D1819: DIC Corporation, CI Pigment Yellow 138 Irgazin Red L3630: DIC Corporation, CI Pigment Red 254 Hostaperm Violet RL 02: SUDARSHAN, CI Pigment Violet 23 FASTOGEN GREEN A110: DIC Corporation, CI Pigment Green 58 FASTOGEN BLUE C500: DIC Corporation, CI Pigment Blue 15:6 <Acidic group-containing pigment dispersing aid> A sulfonated product of CI Pigment Red 2 was prepared using the following method. 30 mL of concentrated sulfuric acid was placed in a 100 mL Erlenmeyer flask, and 10 g of CI Pigment Red 2 was added while stirring with a magnetic stirrer. The mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was placed in a 1 L beaker, and the reaction mixture was poured into the ice water and stirred with a magnetic stirrer for 30 minutes. The mixture was filtered under reduced pressure, washed with water, and the resulting solid was dried to obtain a sulfonated product of CI Pigment Red 2. <Polymer pigment dispersant> LPN21324: BYK Co., Ltd., copolymer containing quaternary ammonium base (graft copolymer containing quaternary amino group), amine value 0 mg KOH / g, solid content 40% by mass

[0099] <Preparation of polymer pigment dispersant> (Polymer pigment dispersant 4-1: (MMA-BMA) / / (DMAEMA BzCl) = (34.4 / 34.4) / / (31.2), polymer pigment dispersant with quaternary ammonium salt group, amine value 0 mg KOH / g, weight average molecular weight 10,000) A degassed glass reactor was charged with 34.4 g of MMA, 34.4 g of BMA, and 1 L of THF, followed by 4.5 mmol of a hexane solution of n-butyllithium (where the random copolymer of MMA and BMA was synthesized). The mixture was then cooled to -78°C and stirred for 2 hours. Next, 17.2 g of DMAEMA was added to synthesize the DMAEMA block moiety bound to the random copolymer of MMA and BMA. After stirring for 2 hours, the reaction was stopped. To this reaction solution, 14.0 g of BzCl and 45.0 g of MeOH, both of which had been previously purged with argon, were added, and the mixture was allowed to react at 60°C for 12 hours.

[0100] (Polymer pigment dispersant 4-2: (MMA-BMA) / / (DMAEMA / DMAEMA·BzCl) = (34.9 / 34.9) / / (1.8 / 28.4), a polymer pigment dispersant having 10% by mass of tertiary amino groups and 90% by mass of quaternary ammonium salt groups, an amine value of 5 mg KOH / g, and a weight-average molecular weight of 10,000) A degassed glass reactor was charged with 34.9 g of MMA, 34.9 g of BMA, and 1 L of THF, followed by 4.5 mmol of a hexane solution of n-butyllithium (where the random copolymer of MMA and BMA was synthesized). The mixture was then cooled to -78°C and stirred for 2 hours. Next, 17.5 g of DMAEMA was added to synthesize the DMAEMA block moiety bound to the random copolymer of MMA and BMA. After stirring for 2 hours, the reaction was stopped. To this reaction solution, 12.7 g of BzCl and 45.0 g of MeOH, both of which had been previously purged with argon, were added, and the mixture was allowed to react at 60°C for 12 hours.

[0101] (Polymer pigment dispersant 4-3: (MMA-BMA) / / (DMAPAA·BzCl) = (34.9 / 34.9) / / (30.2), polymer pigment dispersant with quaternary ammonium salt group, amine value 0 mg KOH / g, weight average molecular weight 10,000) A degassed glass reactor was charged with 34.4 g of MMA, 34.4 g of BMA, and 1 L of THF, followed by 4.5 mmol of a hexane solution of n-butyllithium (where the random copolymer of MMA and BMA was synthesized). The mixture was then cooled to -78°C and stirred for 2 hours. Next, 17.2 g of DMAPAA was added to synthesize the DMAPAA block moiety linked to the random copolymer of MMA and BMA. After stirring for 2 hours, the reaction was stopped. To this reaction solution, 14.0 g of BzCl and 45.0 g of MeOH, both of which had been previously purged with argon, were added, and the mixture was allowed to react at 60°C for 12 hours.

[0102] (Polymer pigment dispersant 4-4: (MMA-BMA-MPEG13A) / / (DMAEMA BzCl) = (25.8 / 25.8 / 17.2) / / (31.2), polymer pigment dispersant with quaternary ammonium salt group, amine value 0 mg KOH / g, weight average molecular weight 10,000) A degassed glass reactor was charged with 25.8 g of MMA, 25.8 g of BMA, 17.2 g of MPEG13A, and 1 L of THF, followed by 4.5 mmol of n-butyllithium in hexane (a random copolymer of MMA, BMA, and MPEG13A was synthesized). The mixture was then cooled to -78°C and stirred for 2 hours. Next, 17.2 g of DMAEMA was added to synthesize the DMAEMA block moiety linked to the MMA and BMA random copolymer. After stirring for 2 hours, the reaction was stopped. To this reaction solution, 14.0 g of BzCl and 45.0 g of MeOH, both of which had been previously purged with argon, were added, and the mixture was allowed to react at 60°C for 12 hours.

[0103] (Polymer pigment dispersant 4-5: (MMA-BMA) / / (DMAEMA / DMAEMA·BzCl) = (37.0 / 37.0) / / (9.3 / 16.7), polymeric pigment dispersant containing 50% by mass of tertiary amino groups and 50% by mass of quaternary ammonium salt groups, amine value 30 mg KOH / g, weight average molecular weight 10,000) A degassed glass reactor was charged with 37.0 g of MMA, 37.0 g of BMA, and 1 L of THF, followed by 4.5 mmol of a hexane solution of n-butyllithium (where the random copolymer of MMA and BMA was synthesized). The mixture was then cooled to -78°C and stirred for 2 hours. Next, 18.5 g of DMAEMA was added to synthesize the DMAEMA block moiety bound to the random copolymer of MMA and BMA. After stirring for 2 hours, the reaction was stopped. To this reaction solution, 7.5 g of BzCl and 25.0 g of MeOH, which had previously been purged with argon, were added, and the mixture was allowed to react at 60°C for 12 hours.

[0104] (Polymer pigment dispersant 3-1: (MMA-BMA) / / (DMAEMA) = (40.0 / 40.0) / / (20.0), polymer pigment dispersant with tertiary amino group, amine value 65 mg KOH / g, weight average molecular weight 10,000) A degassed glass apparatus was charged with 40.0 g of MMA, 40.0 g of BMA, and 1 L of THF, followed by 4.5 mmol of a hexane solution of n-butyllithium (where the random copolymer moiety of MMA and BMA was synthesized). The mixture was then cooled to -78°C and stirred for 2 hours. Next, 20.2 g of DMAEMA was added to synthesize the DMAEMA block moiety bonded to the random copolymer moiety of MMA and BMA. After stirring for 2 hours, the reaction was stopped. The synthesized solution was added dropwise to a large amount of methanol to precipitate the dispersant. The dispersant was collected with filter paper, washed several times with methanol, and dried under reduced pressure at 60°C. The resulting dispersant solution was added to a solvent (PGMEA:PGME = 2:1) to obtain a 40% by mass solution of polymeric pigment dispersant 3-1.

[0105] (Polymer pigment dispersant 3-2: (MMA-BMA) / / (DMAPAA) = (40.0 / 40.0) / / (20.0), polymer pigment dispersant with tertiary amino group, amine value 65 mg KOH / g, weight average molecular weight 10,000) A dispersant solution was obtained in the same manner as for polymeric pigment dispersant 3-1, except that the DMAEMA used in the production of polymeric pigment dispersant 3-1 was changed to DMAPAA. The obtained dispersant solution was added to a solvent (PGMEA:PGME = 2:1) to obtain a 40 mass % solution of polymeric pigment dispersant 3-2.

[0106] (Polymer pigment dispersant 3-3: (MMA-BMA-MPEG13A) / / (DMAEMA) = (30.0 / 30.0 / 20.0) / / (20.0), polymer pigment dispersant with tertiary amino group, amine value 65 mg KOH / g, weight average molecular weight 10,000) A dispersant solution was obtained in the same manner as for polymeric pigment dispersant 3-1, except that the 40.0 g of MMA and 40.0 g of BMA used in the production of polymeric pigment dispersant 3-1 were changed to 30.0 g of MMA, 30.0 g of BMA, and 20.0 g of MPEG13A. The obtained dispersant solution was added to a solvent (PGMEA:PGME = 2:1) to obtain a 40 mass% solution of polymeric pigment dispersant 3-3.

[0107] <First alkali-soluble resin> ZAH-110: Soken Chemical & Engineering Co., Ltd., alkali-soluble acrylic resin, Foret ZAH-110, acid value 100 mg KOH / g, weight-average molecular weight approximately 15,000, solid content 35% by mass <Second alkali-soluble resin> ZCR-1569H: Nippon Kayaku Co., Ltd., alkali-soluble epoxy acrylate resin, KAYARAD ZCR-1569H, acid value 98 mg KOH / g, weight-average molecular weight approximately 4,500, solid content 70% by mass <Photopolymerizable compound> DPHA: Dipentaerythritol hexaacrylate <Photopolymerization initiator> IRGACURE OXE02: BASF Japan Ltd., oxime ester photoinitiator, IRGACURE OXE02 <Surface modifier> MF-554: DIC Corporation, Megafac F-554, fluorine-containing and lipophilic group-containing oligomer, solid content 100% <Solvent> PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate

[0108] <Preparation of Pigment Dispersion Composition for Displays> (Preparation Examples 1 to 13, Comparative Preparation Examples 1 to 4) Various materials were mixed to obtain the compositions shown in Tables 1 and 2 (solid content equivalent, units: mass %) and milled overnight in a bead mill to prepare pigment dispersion compositions for displays of Preparation Examples 1 to 13 and Comparative Preparation Examples 1 to 4. The polymeric pigment dispersant used in Preparation Examples 1, 2, 4, 5, 8, 9, 10, 11, 12, and 13 was the polymeric pigment dispersant (I), the polymeric pigment dispersant used in Preparation Example 3 was the polymeric pigment dispersant (II), and the polymeric pigment dispersant used in Preparation Examples 6 and 7 was the polymeric pigment dispersant (III).

[0109] [Table 1]

[0110]

Table 2

[0111] <Examples 1 to 13, Comparative Examples 1 to 4> (Pigment Dispersion Resist Composition for Display) Various materials were mixed so that the compositions in Tables 3 to 4 (unit: mass%) were obtained, and after uniformly mixing using a high-speed stirrer, they were filtered through a filter with a pore size of 3 μm to obtain pigment dispersion resist compositions for displays of Examples 1 to 13 and Comparative Examples 1 to 4.

[0112] Using the obtained pigment dispersion resist compositions for displays, the change amount of optical density (OD value), breakpoint, development adhesion, viscosity stability, and solvent resistance were evaluated by the following method. The results are shown in Tables 1 to 4.

[0113] <OD value (Optical Density)> Each pigment dispersion resist composition for display was applied onto a glass substrate (manufactured by Corning, Eagle XG) with a spin coater so that the film thickness became 1 μm, pre-baked at 100 °C for 3 minutes, exposed with a high-pressure mercury lamp, and further post-baked at 230 °C for 30 minutes to obtain a resist pattern formed only in the solid part. The optical density (OD value) of each resist pattern in the obtained solid part was measured with a transmission densitometer (Ihac-T5, manufactured by Ihara Electronics Industry Co., Ltd.). The OD value was measured at 8 locations, corrected by the film thickness and pigment concentration, and the average value of the OD values excluding the maximum and minimum values was taken as the optical density. Also, the coating film was scraped with a cutter knife, and the film thickness at the OD value measurement point was measured. Corrected OD value = Measured OD value × 15.0 / Pigment concentration × 1.0 / Measured film thickness value Those with a corrected OD value of 1.2 or more were considered qualified. <Breakpoint and Development Adhesion> The pigment dispersion resist compositions for displays prepared in each of the Examples and Comparative Examples were applied to a glass substrate (EAGLE XG) using a spin coater to a film thickness of 3.5 μm, and then prebaked at 100° C. for 3 minutes. Next, using a photomask having a line pattern with a line width of 1 μm to 100 μm, the resist was exposed to UV light at an integrated dose of 50 mJ / cm using a high-pressure mercury lamp. 2 After that, the film was exposed to light at 1 kgf / cm in a 0.05% aqueous potassium hydroxide solution at 23°C. 2 The time when the development pattern started to appear in the shower development at a pressure of 1 kgf / cm was taken as the breakpoint. In the evaluation of development adhesion, development was stopped when the time reached 1.5 times the breakpoint. 2 The glass substrate was then washed with high-pressure spray water, and the size (μm) of the smallest line pattern remaining on the glass substrate was evaluated. A smallest line pattern size of 20 μm or less was deemed to be acceptable. <Viscosity stability> The pigment dispersion compositions for displays prepared in each of the Examples and Comparative Examples were placed in glass bottles, sealed, and stored for one week at 60° C. Before and after storage, the viscosity at 25° C. was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model RE100L), and the rate of viscosity change was determined and evaluated according to the following evaluation criteria. Viscosity change rate = [(viscosity after 1 week of storage - viscosity before storage) / (viscosity before storage)] Evaluation criteria ○: The viscosity change rate was 10% or less. △: The viscosity change rate was more than 10% and 20% or less. ×: The viscosity change rate exceeded 20%. <Solvent resistance> The pigment-dispersed resist compositions for displays prepared in each example and comparative example were applied to glass substrates (50 mm x 70 mm) using a spin coater to a thickness of 3.5 μm. The substrates were prebaked at 100°C for 2 minutes, then exposed to a high-pressure mercury lamp. They were then postbaked at 230°C for 20 minutes, resulting in a resist pattern consisting only of solid areas. The substrates were cut into 50 mm x 10 mm test pieces. 20 mL of N-methylpyrrolidone (NMP) was placed in a screw bottle and heated to 80°C. The test pieces were then placed in an oven at 80°C for 40 minutes, after which the test pieces were removed from the screw bottle and the eluate was obtained. The absorbance of the eluate was measured using a spectrophotometer (UV-2500PC), and the average absorbance from 300 to 1000 nm was reported as the result. A value of 0.03 or less was considered acceptable.

[0114] [Table 3]

[0115] [Table 4]

[0116] As shown in Tables 1 to 4, the polymeric pigment dispersion compositions of Preparation Examples 1 to 13 of the present invention and the resist compositions of Examples 1 to 13 using them were able to achieve both excellent solvent resistance and breakpoint. Furthermore, the resist films obtained using the resist compositions of Examples 1 to 13 had excellent development adhesion. Furthermore, the resist compositions of Examples 1 to 7 achieved high OD values.

Claims

1. a color pigment, a polymeric pigment dispersant including a nitrogen atom-containing functional group, a first alkali-soluble resin, and a solvent; The pigment dispersion composition for displays, wherein the polymer pigment dispersant is any one of the following (I) to (III): (I) The nitrogen atom-containing functional group of the polymeric pigment dispersant is a quaternary ammonium salt group. (II) The nitrogen atom-containing functional groups of the polymeric pigment dispersant contain 10% by mass or less of tertiary amino groups and 90% by mass or more of quaternary ammonium salt groups. (III) The polymeric pigment dispersant comprises a first polymeric pigment dispersant and a second polymeric pigment dispersant, the nitrogen atom-containing functional group of the first polymeric pigment dispersant is a quaternary ammonium salt group, the nitrogen atom-containing functional group of the second polymeric pigment dispersant is a tertiary amino group, and the content of the first polymeric pigment dispersant in the polymeric pigment dispersant is 50 mass% or more.

2. 2. The pigment dispersion composition for displays according to claim 1, wherein the color pigment comprises lactam black.

3. A display-use pigment dispersion composition according to claim 1 or 2, a second alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, The pigment-dispersed resist composition for displays, wherein the second alkali-soluble resin comprises an alkali-soluble resin having a crosslinking functional group.

4. A resist film formed from the pigment-dispersed resist composition for displays according to claim 3.

Images