TW202146589A - Pigment dispersion composition for black matrix, photo resist composition for black matrix and black matrix wherein the pigment dispersion composition includes a black colorant, a pigment dispersant, a compound, and an organic solvent - Google Patents

Abstract

The present invention provides a pigment dispersion composition for a black matrix, which can form a black matrix having an excellent developability for a photoresist composition of the black matrix and an excellent surface resistance even if a post-bake at a high temperature is performed for a long time. The pigment dispersion composition for the black matrix of the present invention is characterized in comprising a black colorant, a pigment dispersant, a compound, and an organic solvent. The pigment dispersant is an acrylic block copolymer containing nitrogen atoms.

Description

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

The present invention relates to a pigment dispersion composition for a black matrix, a photoresist composition for a black matrix, and a black matrix.

In an image display device using liquid crystal or plasma, etc., a light-shielding film (black matrix) is provided in the gap between the coloring patterns in the display area of the screen or at the edge of the peripheral portion of the display area. In addition, in the liquid crystal display using TFT , a light-shielding film (black matrix) is provided on the outside light side of the TFT, etc. In addition, the light-shielding film (black matrix) mainly helps to prevent the leakage of light from the backlight from being reflected on the screen in the liquid crystal display device, and in the plasma display device, it mainly helps to prevent the smear caused by the turbidity of each color light. Reflected on the screen to improve display characteristics (contrast and color purity).

For example, a color filter for converting white light of a backlight source of a liquid crystal display device into colored light is usually manufactured by the following method: on the surface of a transparent substrate such as a glass or a plastic sheet formed with a black matrix, a stripe or mosaic pattern is formed. Such patterns form pixels of different hues of red, green, and blue in sequence.

Also, in the touch panel in which the image display device and the position input device are superimposed, a color filter formed with a black matrix as a light-shielding film is also used, which is usually formed on the opposite side of the sensor substrate through a cover glass. . However, with the increasing demand for weight reduction of touch panels, in order to further reduce weight, a technology of forming a light-shielding film and a touch sensor on the same side of the cover glass at the same time has been developed.

環之多價

化合物。For example, Patent Document 1 discloses a technique for a photoresist composition for a black matrix comprising a black colorant, an alkali-soluble resin having a carboxyl group, a photopolymerization initiator, an organic solvent,

polyvalent ring

compound.

化合物之黑矩陣用光阻組成物中使用上述碳二亞胺系之顏料分散劑時，有「所得到之黑矩陣其表面電阻値優異，但是黑矩陣用光阻組成物之顯影性降低」之類的課題。In Patent Document 1, a carbodiimide-based pigment dispersant is used as the pigment dispersant. containing polyvalent

When the above-mentioned carbodiimide-based pigment dispersant is used in the black matrix photoresist composition of the compound, there is a problem of "the obtained black matrix has excellent surface resistance value, but the developability of the black matrix photoresist composition is lowered". class subject.

化合物之黑矩陣用光阻組成物中使用一直以來通常被使用之顏料分散劑（例如，胺酯（urethane）系顏料分散劑）時，雖然黑矩陣用光阻組成物之顯影性沒有問題，但有所得到之黑矩陣之表面電阻値降低之類的課題。On the other hand, in the presence of polyvalent

When a conventionally used pigment dispersant (for example, a urethane-based pigment dispersant) is used in the photoresist composition for black matrix of the compound, there is no problem in the developability of the photoresist composition for black matrix. There is a problem such as a reduction in the surface resistance of the obtained black matrix.

In addition, in recent years, video display devices have been used in various applications such as mobile phone applications. With the expansion of the use of such image display devices, a stronger black matrix is gradually required.

As a method of making the black matrix firmer, a method of post-bake at a high temperature and for a long time is sometimes used. However, the conventional pigment dispersions for black matrices have a problem that, when baked at a high temperature and after a long period of time, the surface resistance value is lowered, and there is still room for improvement. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-344996

[The problem to be solved by the invention]

Therefore, an object of the present invention is to provide a pigment-dispersed composition for black matrices, which can form a black matrix having excellent developability as a photoresist composition for black matrices, and excellent surface resistance value even if it is baked at high temperature and after a long period of time. matrix. [Technical means to solve the problem]

化合物、及有機溶劑，且上述顏料分散劑為含有氮原子之丙烯酸系嵌段共聚物，可獲得一種黑矩陣用顏料分散組成物，其能夠形成黑矩陣用光阻組成物之顯影性優異、且即使進行高溫且長時間之後烘烤，表面電阻值亦優異之黑矩陣，從而完成本發明。The inventors of the present invention found that by containing a black colorant, a pigment dispersant,

A compound, and an organic solvent, wherein the pigment dispersant is an acrylic block copolymer containing nitrogen atoms, to obtain a pigment dispersion composition for a black matrix, which can form a photoresist composition for a black matrix, excellent in developability, and The present invention has been completed with a black matrix having excellent surface resistance value even after baking at a high temperature and for a long time.

化合物、及有機溶劑，上述顏料分散劑為含有氮原子之丙烯酸系嵌段共聚物。That is, the present invention is a pigment dispersion composition for a black matrix, characterized by comprising a black colorant, a pigment dispersant,

A compound and an organic solvent, wherein the pigment dispersant is a nitrogen atom-containing acrylic block copolymer.

化合物較佳為下述通式（1）及/或（2）所表示之化合物。

〔通式（1）中，R¹ 及R² 表示可具有不飽和鍵之烷基或芳基，彼此可相同亦可不同。X¹ 為2價連結基。 通式（2）中，R³ 及R⁴ 表示可具有不飽和鍵之烷基或芳基，彼此可相同亦可不同。X² 為2價連結基。〕 又，上述黑色著色劑較佳含有碳黑。 又，上述碳黑較佳為酸性碳黑。 本發明亦為由本發明之黑矩陣用顏料分散組成物得到之黑矩陣用光阻組成物。 本發明亦為由本發明之黑矩陣用光阻組成物形成之黑矩陣。 以下對本發明之黑矩陣用顏料分散組成物、黑矩陣用光阻組成物、及由此形成之黑矩陣進行詳細說明。In the pigment dispersion composition for black matrices of the present invention, it is preferable to further contain a pigment dispersion auxiliary. Moreover, it is preferable that the said pigment dispersing auxiliary agent is a phthalocyanine compound. Also, the above

The compound is preferably a compound represented by the following general formula (1) and/or (2).

[In the general formula (1), R ¹ and R ² represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same or different from each other. X ¹ is a divalent linking group. In the general formula (2), R ³ and R ⁴ represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same or different from each other. X ² is a divalent linking group. ] Moreover, it is preferable that the said black coloring agent contains carbon black. Moreover, it is preferable that the said carbon black is acidic carbon black. The present invention is also a photoresist composition for a black matrix obtained from the pigment dispersion composition for a black matrix of the present invention. The present invention is also a black matrix formed from the photoresist composition for a black matrix of the present invention. Hereinafter, the pigment dispersion composition for black matrices, the photoresist composition for black matrices, and the black matrix formed therefrom of the present invention will be described in detail.

化合物、及有機溶劑，上述環氧樹脂具有芳香環。<Pigment dispersion composition for black matrix> The pigment dispersion composition for black matrix of the present invention is characterized by containing a black colorant, an epoxy resin,

The compound, and the organic solvent, wherein the epoxy resin has an aromatic ring.

(black colorant) The pigment dispersion composition for black matrices of the present invention contains a black colorant. As said black coloring agent, it is preferable to contain carbon black, and it is more preferable that the said carbon black is acidic carbon black. The carbon black is preferably an average primary particle size of 20 to 60 nm, and more preferably neutral carbon black with an average primary particle size of 20 to 60 nm and/or acid carbon black with an average primary particle size of 20 to 60 nm. When the primary particle diameter of the above-mentioned black colorant is less than 20 nm or more than 60 nm, sufficient light-shielding properties may not be obtained or storage stability may be deteriorated. In addition, the said average primary particle diameter is the value of the arithmetic mean diameter obtained by electron microscope observation.

When the above neutral carbon black and acid carbon black are used together, the mixing ratio (mass ratio) of neutral carbon black and acid carbon black is preferably 85/15 to 15/85, more preferably 75/25 to 40/ 60. In the case where the ratio of neutral carbon black in the above carbon black is more than 85/15, there is a case where the sealing strength is lowered, and when the ratio of acid carbon black is more than 15/85, there is a development margin or a thin line. When the adhesion is reduced.

The above-mentioned acidic carbon black and neutral carbon black will be described. Carbon black can be roughly divided into acidic carbon and neutral carbon according to the structure of the surface. Acidic carbon refers to carbonaceous substances that are originally acidic or acidified by artificial treatment, and show acidity when they are mixed with distilled water and boiled. On the other hand, neutral carbons are known to exhibit a neutral or higher pH when mixed with distilled water and boiled.

The neutral carbon black preferably has a pH in the range of 8.0 to 10.0, and specifically, Printex 25 (average primary particle size 56 nm, pH 9.5), Printex 35 (average primary particle size 56 nm, pH 9.5) manufactured by Orion Engineered Carbons, Inc., Primary particle size: 31 nm, pH 9.5), Printex 65 (average primary particle size: 21 nm, pH 9.5), MA#20 manufactured by Mitsubishi Chemical Corporation (average primary particle size: 40 nm, pH 8.0), MA#40 (average primary particle size 40 nm, pH 8.0), MA#30 (average primary particle size 30 nm, pH 8.0), etc.

As the acid carbon black, the pH is preferably in the range of 2.0 to 4.0. Specifically, Raven 1080 (average primary particle size: 28 nm, pH 2.4), Raven 1100 (average primary particle size) manufactured by Columbia Chemicals, Inc. Diameter 32 nm, pH 2.9), MA-8 (average primary particle size 24 nm, pH 3.0) manufactured by Mitsubishi Chemical Corporation, MA-100 (average primary particle size 22 nm, pH 3.5), Orion Engineered Carbons Special black 250 (average primary particle size 56 nm, pH 3.0), Special black 350 (average primary particle size 31 nm, pH 3.0), Special black 550 (average primary particle size 25 nm, pH 4.0), etc. .

As the above-mentioned black colorant, Special black 250 is preferable from the viewpoint of appropriately imparting pigment dispersibility and surface resistance value.

Furthermore, the above pH can be measured by the following method: adding 1 g of carbon black to 20 ml of distilled water (pH 7.0) after removing carbonic acid, and mixing with a magnetic stirrer to prepare an aqueous suspension, using The glass electrode was measured at 25°C (DIN ISO 787/9).

The content of the black colorant is preferably 3 to 70% by mass, more preferably 10 to 50% by mass, expressed as a percentage by mass relative to the total solid content of the pigment dispersion composition for black matrices of the present invention. If the content of the black colorant is less than 3% by mass, the light-shielding properties at the time of forming a black matrix may be lowered, and if it exceeds 70% by mass, the pigment may be difficult to disperse.

化合物，而藉由後烘烤時之高溫，上述㗁

化合物聚合而成為高分子量體，藉此，即使因高溫而軟化之塗膜中產生上述黑色著色劑之移動，亦由於該㗁

化合物之聚合物成為間隔物，而上述黑色著色劑彼此不接觸。 又，上述顏料分散劑由於對上述黑色著色劑之吸附強烈，因此和上述

化合物之聚合物相同，由於成為間隔物，而上述黑色著色劑彼此不接觸。 因此，推定本發明之黑矩陣用光阻組成物中，由於不形成導電性之組織結構，故可確保高表面電阻值。 但本發明可不限定於該作用機制而解釋。(Pigment Dispersant) The pigment dispersion composition for a black matrix of the present invention contains a pigment dispersant. The above-mentioned pigment dispersant is an acrylic block copolymer containing nitrogen atoms. By containing the above-mentioned pigment dispersant and the following

compound, and by the high temperature during post-baking, the above

The compound is polymerized to form a high-molecular-weight body, so that even if the above-mentioned movement of the black colorant occurs in the coating film softened by high temperature, the

The polymer of the compound becomes a spacer, and the above-mentioned black colorants do not come into contact with each other. In addition, since the above-mentioned pigment dispersant strongly adsorbs the above-mentioned black colorant, it is different from the above-mentioned

The polymers of the compounds are the same, and the above-mentioned black colorants do not come into contact with each other because they serve as spacers. Therefore, in the photoresist composition for a black matrix of the present invention, it is presumed that a high surface resistance value can be ensured because a conductive structure is not formed. However, the present invention can be interpreted without being limited to this mechanism of action.

As the above-mentioned nitrogen atom-containing acrylic block copolymer, those disclosed in JP 2019-35970 A and the production method can be appropriately selected and used. As the above-mentioned nitrogen atom-containing acrylic block copolymer, specifically, the A block having at least one of a quaternary ammonium salt group and an amine group in the side chain, and a block not having a quaternary ammonium salt group and The B block structure of the amine group is more preferably at least one of an AB block copolymer and a BAB block copolymer.

The amine value of the nitrogen atom-containing acrylic block copolymer is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g. In addition, the amine value is the value expressed in mg of KOH corresponding to the molar equivalent of the acid required to neutralize the amine groups in 1 g of the acrylic block copolymer.

The molecular weight of the nitrogen atom-containing acrylic block copolymer is preferably 1,000 to 40,000, more preferably 2,000 to 20,000 in terms of weight average molecular weight (Mw) in terms of polystyrene measured by GPC.

As a commercial item of the said nitrogen atom containing acrylic block copolymer, BYK-LPN21116, BYK-2000, BYK-LPN6919, BYK-LPN21324, BYK-LPN22012 (all are BYK-Chemie company make) etc. are mentioned.

As content of the said pigment dispersing agent, 1-200 mass parts is preferable with respect to 100 mass parts of said black coloring agents, More preferably, it is 5-100 mass parts.

化合物） 本發明之黑矩陣用顏料分散組成物含有㗁

化合物。 上述

化合物較佳為下述通式（1）及/或（2）所表示之化合物。

[通式（1）中，R¹ 及R² 表示可具有不飽和鍵之烷基或芳基，彼此可相同亦可不同。X¹ 為2價連結基。 通式（2）中，R³ 及R⁴ 表示可具有不飽和鍵之烷基或芳基，彼此可相同亦可不同。X² 為2價連結基。](㗁

compound) The pigment dispersion composition for black matrix of the present invention contains:

compound. the above

The compound is preferably a compound represented by the following general formula (1) and/or (2).

[In the general formula (1), R ¹ and R ² represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same or different from each other. X ¹ is a divalent linking group. In the general formula (2), R ³ and R ⁴ represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same or different from each other. X ² is a divalent linking group. ]

R ¹ and R ² and R ³ and R ⁴ are an alkyl group or an aryl group which may have an unsaturated bond. The above-mentioned alkyl group may be, for example, any of linear, branched, and cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-propyl Butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. or from cashew nut shell liquid (CNSL) Alkyl groups with unsaturated bonds, etc.

As said aryl group, a tolyl group, a xylyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned, for example.

X ¹ and X ² are divalent linking groups. As the above-mentioned divalent linking group, in addition to the linking groups represented by the following formulae (3) to (5), a linear or branched alkylene group having 1 to 12 carbon atoms may be mentioned; One or more -CH ₂ - of the alkylene group is substituted by -O-, -S-, -NH-, urethane group, urea group, amide group, siloxane bond which may have a substituent, or -CO- The bivalent linking base, etc.

化合物，就形成表面電阻值高之黑矩陣之觀點而言，較佳為R¹ 及R² 為苯基且X¹ 為上述式（3）～（5）所示之連結基之任一者。 又，作為上述通式（2）所表示之㗁

化合物，就形成表面電阻值高之黑矩陣之觀點而言，較佳為R³ 及R⁴ 為H且X² 為亞甲基二氧基，或者R³ 及R⁴ 為來自腰果殼液（CNSL）之可具有不飽和鍵之烷基且X² 為伸乙基。As represented by the general formula (1) above

In the compound, from the viewpoint of forming a black matrix having a high surface resistance value, it is preferable that R ¹ and R ² are phenyl groups, and X ¹ is any one of the linking groups represented by the above formulae (3) to (5). In addition, as the expression represented by the above general formula (2)

Compounds, from the viewpoint of forming a black matrix with a high surface resistance value, preferably R ³ and R ⁴ are H and X ² are methylene dioxy, or R ³ and R ⁴ are derived from cashew nut shell liquid (CNSL ) may have an alkyl group with an unsaturated bond and X ² is an ethylidene group.

化合物之方法，可使用公知之方法，例如可使用日本特開2000-178332號公報、日本特開2003-344996號公報等中記載之方法。as obtained above 㗁

As the method of the compound, a known method can be used, for example, the method described in JP 2000-178332 A, JP 2003-344996 A, and the like can be used.

化合物之含量，就較佳地形成即使進行高溫且長時間之後烘烤，表面電阻值亦不會降低之黑矩陣之觀點而言，以相對於本發明之黑矩陣用顏料分散組成物之全部固形物成分之質量百分率表示，較佳為下限為0.1質量%，更佳為下限為0.5質量%，再更佳為下限為1質量%，尤佳為下限為3質量%，最佳為下限為5質量%。 又，作為上述㗁

化合物之含量，就確保黑矩陣內之源自顏料濃度之光學濃度的觀點而言，以相對於本發明之黑矩陣用顏料分散組成物之全部固形物成分之質量百分率表示，較佳為上限為30質量%，更佳為上限為25質量%，再更佳為上限為20質量%，尤佳為上限為15質量%。as the above

The content of the compound is relative to the total solid content of the pigment dispersion composition for black matrix of the present invention, from the viewpoint of preferably forming a black matrix whose surface resistance value does not decrease even after baking at a high temperature and for a long time. Indicated by the mass percentage of the material components, preferably the lower limit is 0.1 mass %, more preferably the lower limit is 0.5 mass %, still more preferably the lower limit is 1 mass %, particularly preferably the lower limit is 3 mass %, and the best lower limit is 5 mass % quality%. Also, as the above

The content of the compound, from the viewpoint of securing the optical density derived from the pigment concentration in the black matrix, is expressed as a mass percentage relative to the total solid content of the pigment dispersion composition for a black matrix of the present invention, and the upper limit is preferably 30 mass %, more preferably the upper limit is 25 mass %, still more preferably the upper limit is 20 mass %, and particularly preferably the upper limit is 15 mass %.

(Organic solvents) The pigment dispersion composition for black matrices of the present invention contains an organic solvent. As the above-mentioned organic solvent, the organic solvent conventionally used in the field of liquid crystal black matrix photoresist can be preferably used.

Examples of the organic solvent, specifically, having a boiling point in a normal pressure (1.013 × 10 ² kPa) of the ester 100 ~ 250 ℃ of an organic solvent, an ether-based organic solvents, ether ester organic solvents, ketone organic solvents, aromatic Hydrocarbon-based organic solvents, nitrogen-containing organic solvents, etc. If a large amount of the above-mentioned organic solvent with a boiling point exceeding 250°C is contained, there is a case in which the coating film formed by coating the photoresist composition for black matrix obtained from the pigment dispersion composition for black matrix of the present invention is subjected to pre-baking (pre-baking). -bake), the organic solvent is not sufficiently evaporated and remains in the dry coating film, thereby reducing the heat resistance of the dry coating film. Moreover, when a large amount of the organic solvent whose boiling point is less than 100 degreeC is contained, it becomes difficult to apply|coat uniformly without unevenness, and the coating film excellent in surface smoothness may not be obtained.

Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethyl ether. Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and other ether-based organic solvents; Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other ether ester organic solvents; Ketone-based organic solvents such as isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ester-based organic solvents such as ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl formate, etc.; alcohol-based solvents such as methanol, ethanol, isopropanol, butanol; N-methyl alcohol Nitrogen-containing organic solvents such as pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These can be used individually or in mixture of 2 or more types.

Among the above-mentioned organic solvents, in terms of solubility, dispersibility, coatability, etc., diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and ethylene glycol monomethyl ether acetate are preferred , propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxy propionate Butyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc., more preferably propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

(Pigment Dispersing Auxiliary) The pigment dispersion composition for a black matrix of the present invention preferably contains a pigment dispersion auxiliary. In the step of micronizing or dispersing the above-mentioned black colorant, the acid group increases the affinity with the organic solvent or the pigment dispersant due to the adsorption of the basic skeleton part and the surface of the pigment, so it can improve the dispersion of the above-mentioned black colorant. Effects such as miniaturization over time or dispersion stability over time after dispersion. In addition, the above-mentioned black colorant dispersing aid itself is dissolved in an organic solvent or in a dispersed state in the form of fine particles, since it can be adsorbed in a wider range on the surface of the above-mentioned black colorant, so it is more suitable.

As said pigment dispersing aid, the phthalocyanine type compound which has an acid group, the anthraquinone type compound which has an acid group, the naphthalene type compound which has an acid group, etc. are illustrated. Among them, a phthalocyanine-based compound having an acid group is preferred from the viewpoint of the dispersibility of the black colorant.

As said acid group, a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. are mentioned. Among them, a sulfonic acid group is preferable from the viewpoint of the dispersibility of the black colorant and the viewpoint of appropriately imparting a surface resistance value to the black matrix.

As a commercial item of the phthalocyanine type compound which has the said acid group, BYK-2100 (made by BYK-Chemie company), Solsperse 5000 (made by Lubrizol company), etc. are mentioned.

About content of the said pigment derivative, 0.1-20 mass parts is preferable with respect to 100 mass parts of said black colorants, More preferably, it is 0.5-10 mass parts.

(Pigment dispersion composition for black matrix) The viscosity of the pigment dispersion composition for a black matrix of the present invention is preferably 10 mPa･s or less, more preferably 8 mPa･s or less, and still more preferably 6 mPa･s or less. In addition, the above viscosity means the viscosity measured at 25°C using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., R100 type viscometer type RE100L).

The viscosity change rate before and after the pigment dispersion composition for black matrix of the present invention is stored at 40°C for 1 month [(viscosity after storage - viscosity before storage)/(viscosity before storage)] is preferably 10% or less, More preferably, it is 8% or less, and still more preferably, it is 6% or less.

(Manufacturing method of pigment dispersion composition for black matrix) As a method for producing the pigment dispersion composition for black matrix of the present invention, it can be obtained by adding the above-mentioned various components, mixing and kneading. The method for performing the above-mentioned kneading is not particularly limited, and for example, a bead mill, a ready mill, an ultrasonic homogenizer, a high pressure homogenizer, a paint shaker, a ball mill, and a roll mill can be used. , sand mill, sand mill, dyno-mill, dispermat, SC mill, nanomizer, etc., are kneaded by known methods.

<Photoresist composition for black matrix> The present invention is also a photoresist composition for a black matrix obtained from the pigment dispersion composition for a black matrix of the present invention.

(Pigment dispersion composition for black matrix) The photoresist composition for black matrices of the present invention contains the above-described pigment dispersion composition for black matrices of the present invention. As content of the said pigment dispersion composition for black matrices, based on the total mass of the photoresist composition for black matrices of this invention, it is preferable that it is 30-80 mass %, and it is more preferable that it is 40-75 mass %.

、2-氯9-氧硫

、1-羥基環己基苯基酮、第三丁基蒽醌、1-氯蒽醌、2,3-二氯蒽醌、3-氯-2-甲基蒽醌、2-乙基蒽醌、1,4-萘醌、1,2-苯并蒽醌、1,4-二甲基蒽醌、2-苯基蒽醌、2-甲基-1[4-（甲硫基）苯基]-2-

啉基丙烷-1-酮等二苯甲酮系、9-氧硫

系、蒽醌系、三

系等光聚合起始劑等。 上述光聚合起始劑可單獨使用或將2種以上加以組合而使用。(Photopolymerization Initiator) The photoresist composition for a black matrix of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can generate radicals or cations by irradiation with active energy rays such as ultraviolet rays or electron beams. For example, 1-[9-ethyl-6 -(2-Methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, benzophenone, N,N'-tetraethyl-4 ,4'-Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isoform Butyl ether, benzil dimethyl ketal, α-hydroxyisobutylphenone, 9-oxysulfur

, 2-chloro-9-oxosulfur

, 1-hydroxycyclohexyl phenyl ketone, 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-

Benzophenones such as linopropane-1-one, 9-oxosulfur

series, anthraquinone series, three

such as photopolymerization initiators, etc. The above-mentioned photopolymerization initiators may be used alone or in combination of two or more.

The content of the above-mentioned photopolymerization initiator is represented by a mass percentage relative to the total solid content of the photoresist composition for a black matrix of the present invention, and is preferably 1 to 20 mass %.

(Photopolymerizable compound) The photoresist composition for a black matrix of the present invention preferably contains a photopolymerizable compound. As said photopolymerizable compound, the monomer which has 1 or 2 or more of photopolymerizable unsaturated bonds in a molecule|numerator, the oligomer which has a photopolymerizable unsaturated bond, etc. are mentioned.

As the monomer having one photopolymerizable unsaturated bond in the molecule, for example, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, and butyl acrylate can be used. , 2-ethylhexyl acrylate and other alkyl methacrylates or alkyl acrylates; benzyl methacrylate, benzyl acrylate and other aralkyl methacrylates or aralkyl acrylates; butoxy methacrylate Ethyl methacrylate, butoxyethyl acrylate and other alkoxyalkyl methacrylate or alkoxyalkyl acrylate; N,N-dimethylaminoethyl methacrylate, N,N-dimethylacrylate Amino ethyl ester and other amino alkyl methacrylates or acrylic acid amino alkyl esters; polyalkylene glycol monoalkanes such as diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc. methacrylates or acrylates of base ethers; methacrylates or acrylates of polyalkylene glycol monoaryl ethers such as hexaethylene glycol monophenyl ether; isocamphenyl methacrylate or isocamphenyl acrylate ; Glyceryl methacrylate or glycerol acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate, etc.

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 can be used. Alcohol Dimethacrylate, Diethylene Glycol Dimethacrylate, Glycerin Dimethacrylate, Neopentyl Glycol Dimethacrylate, Polyethylene Glycol Dimethacrylate, Polypropylene Glycol Dimethacrylate Esters, Tetraethylene Glycol Dimethacrylate, Trimethylolpropane Trimethacrylate, Neotaerythritol Trimethacrylate, Neotaerythritol Tetramethacrylate, Dipionaerythritol Tetramethyl Alkyl acrylate, Dipivalerythritol Hexamethacrylate, Dipivalerythritol Pentamethacrylate, Bisphenol A Diacrylate, 1,4-Butanediol Diacrylate, 1,3-Butanediol Alcohol Diacrylate, Diethylene Glycol Diacrylate, Glycerin Diacrylate, Neopentyl Glycol Diacrylate, Polyethylene Glycol Diacrylate, Polypropylene Glycol Diacrylate, Tetraethylene Glycol Diacrylate, Trihydroxy Methylpropane triacrylate, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, dipivalerythritol tetraacrylate, dipivalerythritol hexaacrylate, dipivalerythritol pentaacrylate, etc. .

As the oligomer having the above-mentioned photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the above-mentioned monomer can be used. The said photopolymerizable compound can be used individually or in combination of 2 or more types.

Content of the said photopolymerizable compound is represented by the mass percentage with respect to the total solid content of the photoresist composition for black matrices of this invention, Preferably it is 3-50 mass %.

(alkali-soluble resin) The photoresist composition for a black matrix of the present invention preferably contains an alkali-soluble resin. The alkali-soluble resin is preferably one that acts as a binder for the black colorant and is soluble in a developing solution, especially an alkaline developing solution, used in the development process when a black matrix is produced.

As said alkali-soluble resin, a block copolymer can be used. By using the block copolymer, the dispersibility of the pigment is improved compared with other copolymers, and the solubility to PGMEA or alkaline developer can be imparted. Among the block copolymers, it is preferable to have "a block composed of an ethylenically unsaturated monomer having one or more carboxyl groups" and "a block composed of other copolymerizable ethylenically unsaturated monomers" of block copolymers.

There is no restriction|limiting in particular as said block copolymer, The conventional user can be used. Among them, specifically, ethylenically unsaturated monomers having a carboxyl group such as acrylic acid and methacrylic acid, and styrene and 2-hydroxyethyl acrylate that can be copolymerized with an ethylenically unsaturated monomer having a carboxyl group can be mentioned. , 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, methyl methacrylate Monomers and oligomers such as glyceryl methacrylate, N-phenylmaleimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, carbon epoxy diacrylate, etc. A copolymer of at least one ethylenically unsaturated monomer in the group. Among them, it is preferable not to use N-vinylpyrrolidone and a monomer containing a sulfur element. As the above-mentioned block copolymer, a block resin synthesized by living radical polymerization or anionic polymerization can be used. A part of the block portion of the above-mentioned block copolymer may be constituted by a random copolymer.

As the above-mentioned alkali-soluble resin, an alkali-soluble Cardo resin can also be used. As said alkali-soluble Cardo resin, the epoxy (meth)acrylate which has a perylene skeleton which is an addition product of a perylene epoxy (meth)acrylic acid derivative and a dicarboxylic anhydride and/or a tetracarboxylic dianhydride can be mentioned. Acid adducts, etc. Moreover, this alkali-soluble resin may have a photopolymerizable functional group.

The acid value of the above-mentioned 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, still more preferably 10 to 200 mgKOH/g, from the viewpoint of developing characteristics. It is 60～150 mgKOH/g. In addition, in this specification, the said acid value is a theoretical acid value, and is a value calculated|required based on the ethylenically unsaturated monomer which has a carboxyl group, and its content.

The weight-average molecular weight of the alkali-soluble resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 5,000 to 30,000, from the viewpoint of developing characteristics or solubility in organic solvents. In addition, in this invention, the said weight average molecular weight is the weight average molecular weight based on the polystyrene conversion obtained by GPC. In this specification, Water2690 (manufactured by Waters Corporation) was used as an apparatus for measuring the above-mentioned weight average molecular weight, and PLgel 5 μm MIXED-D (manufactured by Agilent Technologies) was used as a column.

About content of the said alkali-soluble resin, 1-200 mass parts is preferable with respect to 100 mass parts of said black colorants, and 10-150 mass parts is still more preferable. In this case, if the content of the above-mentioned alkali-soluble resin is less than 1 part by mass, the developing characteristics may decrease, and if the content of the above-mentioned alkali-soluble resin exceeds 200 parts by mass, the concentration of the above-mentioned black colorant is relatively reduced, so there is a It is difficult to achieve the target color density as a thin film.

It is preferable that the said alkali-soluble resin does not contain any one of primary, secondary, and tertiary amine groups, and further does not contain quaternary ammonium groups. More preferably, it also does not have a basic group. Furthermore, an alkali-soluble resin having a structure other than the block copolymer can be blended within a range that does not impair the effects of the present invention.

(Organic solvents) As said organic solvent, the organic solvent described in the said pigment dispersion composition for black matrices of this invention can be suitably selected and used.

As content of the said organic solvent, based on the total mass of the photoresist composition for black matrices of this invention, it is preferable that it is 1-40 mass %, and it is more preferable that it is 5-35 mass %.

(other additives) The photoresist composition for black matrices of the present invention may appropriately use various additives such as thermal polymerization inhibitors, ultraviolet absorbers, and antioxidants as necessary.

(Photoresist composition for black matrix) The photoresist composition for a black matrix of the present invention is excellent in solubility to a developer. The photoresist composition for black matrix of the present invention was coated on a glass substrate (Corning 1737) with a thickness of 1 μm using a spin coater, and after pre-baking at 100° C. for 3 minutes, it was immersed in 23 The developing solution (0.05 mass % aqueous solution of potassium hydroxide) of ℃, in this case, it is preferable that it dissolves easily.

The photoresist composition for a black matrix of the present invention is excellent in developability. The above-mentioned developability can be tested by the following method. The pigment dispersion photoresist composition for black matrix was apply|coated on the glass substrate (Corning 1737) by the spin coater so that a film thickness might become 1 micrometer, and prebaked at 100 degreeC for 3 minutes. Next, using a mask having line patterns of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm, exposure was performed ^{with a high-pressure mercury lamp with a cumulative UV light amount of 400 mJ/cm 2 .} Then, it was immersed in a developing solution (a 0.05 mass % aqueous solution of potassium hydroxide) at 23° C., and the time (break point) at which a developed pattern started to appear under a spray developing pressure of ^{0.5 kgf/cm 2 was measured.} . At this time, the photoresist composition for the black matrix of the above-mentioned mask portion is preferably completely removed within 60 seconds, more preferably within 45 seconds, and even more preferably within 30 seconds.

化合物、上述顏料分散助劑等。(Manufacturing method of photoresist composition for black matrix) As a manufacturing method of the photoresist composition for black matrix of the present invention, for example, it can be produced by the following method: producing the pigment dispersion composition for black matrix of the present invention, and then, Add the remaining materials, and use a stirring device or the like to stir and mix. The method of stirring and mixing is not particularly limited, and 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. Furthermore, when producing the photoresist composition for black matrices of the present invention, the above-mentioned black colorant, the above-mentioned pigment dispersant, the above-mentioned pigment dispersion agent described in the pigment-dispersed composition for black matrices of the present invention may also be added as necessary.

Compounds, the above-mentioned pigment dispersing aids, and the like.

＜Black Matrix＞ The black matrix of the present invention is formed from the photoresist composition for a black matrix of the present invention.

The method for forming the black matrix of the present invention is not particularly limited. For example, the photoresist composition for a black matrix of the present invention can be coated on a transparent substrate, dried to form a coating film, and then placed on the coating film. A photomask, through which a black matrix is formed by image exposure, development, and photohardening as needed.

About the method of coating, drying, exposing and developing the photoresist composition for black matrices of this invention, a well-known method can be suitably selected. Moreover, as said transparent substrate, a well-known transparent substrate, such as a glass substrate and a plastic substrate, can be suitably selected and used.

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 in terms of the film thickness after drying. By setting it as the said thickness range, a specific pattern can be developed favorably, and a specific optical density can be given favorably.

The black matrix of the present invention was coated on a glass substrate (Corning 1737), pre-baked at 100° C. for 3 minutes, then exposed with a high-pressure mercury lamp (UV cumulative light amount of 400 mJ/cm ² ), and further heated at 230° C. After 3 hours of post-baking, a photoresist pattern with a thickness of 1 μm is formed. At this time, the surface resistance value is preferably 5.0×10 ⁹ Ω/□ or more, more preferably 1.0×10 ^{1 0} Ω/□ or more, and more best of 1.0 × 10 ^{1 1} Ω / □ or more, and particularly preferably 5.0 × 10 ^{1 1} Ω / □ or more, most preferably 1.0 × 10 ¹² Ω / □ or more. Furthermore, the above-mentioned surface resistance value can be measured by using the body: micro current meter R8340, and optional parts (option): shield box (Shield box) R12702A (both are manufactured by Advance Company).

The pigment dispersion composition for black matrix, the photoresist composition for black matrix, and the black matrix of the present invention have the above-mentioned characteristics, so they can be preferably used as a black matrix of an image display device or a touch panel. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, the pigment dispersion composition for black matrices which can form the black matrix which is excellent in the developability of the photoresist composition for black matrices, and is excellent in surface resistance value even if it bakes after a high temperature and a long time can be provided.

The present invention will be specifically described below using examples, but the present invention is not limited to these examples unless it deviates from the gist and scope of application. In addition, unless otherwise stated, in this Example, "part" and "%" represent "mass part" and "mass %", respectively.

化合物＞ （㗁

化合物1） 上述通式（2）中，R³ 及R⁴ 為H且X² 為亞甲基二氧基所表示之㗁

化合物（商品名「JBZ-OP100N」、JFE化學公司製造） （㗁

化合物2） 藉由公知之方法（日本特開2000-178332號公報等中記載之方法）合成上述通式（1）中R¹ 及R² 為苯基且X¹ 為上述式（3）所表示之連結基之㗁

化合物。 （㗁

化合物3） 上述通式（2）中R³ 及R⁴ 為來自腰果殼液（CNSL）之可具有不飽和鍵之烷基且X² 為伸乙基所表示之㗁

化合物（商品名「CR-276」、東北化工公司製造） ＜有機溶劑＞ PM（丙二醇單甲醚） PGMEA（丙二醇單甲醚乙酸酯） ＜光聚合性化合物＞ DPHA（二新戊四醇六丙烯酸酯） ＜光聚合起始劑＞ OXE02（製品名「Irgacure OXE02」、1-[9-乙基-6-（2-甲基苄醯基）-9H-咔唑-3-基]-1-（O-乙醯基肟）乙酮、BASF公司製造） ＜鹼可溶性樹脂＞ WR-301（製品名「WR-301」、Cardo系樹脂、酸值100mgKOH/g、固形物成分45%、ADEKA公司製造）Various materials used in the following Examples and Comparative Examples are as follows. <Black colorant> (Carbon black 1) Acidic carbon black, product name "SPECIAL BLACK 250", average primary particle size 56 nm, pH 3.0, manufactured by Orion Engineered Carbons (carbon black 2) Neutral carbon black, product name "Printex35", average primary particle size 31nm, pH 9.5, manufactured by Orion Engineered Carbons <Pigment Dispersant> (Pigment Dispersant 1) Product name "BYK-LPN21116", consisting of Acrylic AB block copolymer composed of "A block of amine group" and "B block without quaternary ammonium salt group and amine group", solid content 40%, manufactured by BYK-Chemie (Pigment Dispersant 2 ) Product name "BYK-2000", acrylic AB block copolymer composed of "A block with quaternary ammonium salt group in the side chain" and "B block without quaternary ammonium salt group", solid Material composition 40%, manufactured by BYK-Chemie (Pigment Dispersant 3) 50.0 parts equivalent of carbodiimide having an isocyanato group was added to a four-necked flask equipped with a reflux cooling tube, a nitrogen gas introduction tube, a stirring bar, and a thermometer 316 polycarbodiimide compound, 115.7 parts of diol poly(3-methylamyl adipate) with molecular weight of 1000, and kept at about 100 ° C for 5 hours to make the isocyanate group react with the hydroxyl group, and then, 84.6 parts of a ring-opening polymer of polycaprolactone with a molecular weight of 2000 having a carboxyl group at the end was added, and kept at about 100° C. for 2 hours to make the carbodiimide group react with the carboxyl group, after which 375.5 parts of propylene glycol monomethyl was added ether acetate to obtain a solution (solid content 40%) of pigment dispersant 3 with a number average molecular weight of about 4200 and a carbodiimide equivalent of 1583. (Pigment dispersant 4) Product name "DISPERBYK-167", urethane-based pigment dispersant, solid content 52%, manufactured by BYK-Chemie <Pigment Dispersion Aid> (Pigment Dispersion Aid 1) Product name "BYK- 2100", a phthalocyanine compound, manufactured by BYK-Chemie (pigment dispersing aid 2), product name "Solsperse 5000", a phthalocyanine compound, manufactured by Lubrizol (pigment dispersing aid 3) 30ml The concentrated sulfuric acid was added to a 100ml conical flask, while stirring with a magnetic stirrer, 10g of CI Pigment Red 2 was added, and the mixture was stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was added to a 1 L beaker, the above-mentioned reactants were poured into the ice water, and the mixture was stirred with a magnetic stirrer for 30 minutes. This was filtered under reduced pressure, washed with water, and the obtained solid was dried to obtain 12 g of CI Pigment Red 2 slag (pigment dispersing aid 3). ＜㗁

Compound > (㗁

Compound 1) In the above general formula (2), R ³ and R ⁴ are H and X ² is represented by methylene dioxy

Compound (trade name "JBZ-OP100N", manufactured by JFE Chemical Co., Ltd.) (㗁

Compound 2) is synthesized by a known method (the method described in Japanese Patent Laid-Open No. 2000-178332, etc.) wherein R ¹ and R ² in the above general formula (1) are phenyl groups and X ¹ is represented by the above formula (3) the link base

compound. (㗁

Compound 3) In the above general formula (2), R ³ and R ⁴ are alkyl groups that may have unsaturated bonds derived from cashew nut shell liquid (CNSL) and X ² is represented by ethylidene

Compound (trade name "CR-276", manufactured by Tohoku Chemical Co., Ltd.) <Organic solvent> PM (Propylene Glycol Monomethyl Ether) PGMEA (Propylene Glycol Monomethyl Ether Acetate) Acrylate) <Photopolymerization initiator> OXE02 (product name "Irgacure OXE02", 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1 -(O-Acetyl oxime) ethyl ketone, manufactured by BASF Corporation) <Alkali-soluble resin> WR-301 (product name "WR-301", Cardo-based resin, acid value 100 mgKOH/g, solid content 45%, ADEKA company manufacturing)

化合物1～3及有機溶劑加以混合，利用珠磨機混練一晝夜，製成黑矩陣用顏料分散組成物。<Preparation of pigment dispersion composition for black matrix> The above-mentioned black colorant, pigment dispersing agents 1 to 4, pigment dispersing aids 1 to 3,

Compounds 1 to 3 and an organic solvent were mixed and kneaded with a bead mill all day and night to prepare a pigment dispersion composition for a black matrix.

<Evaluation test> (viscosity) For the pigment dispersion compositions for black matrices prepared in Examples and Comparative Examples, the viscosity at 25°C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., R100-type viscometer type RE100L). The results are shown in Table 1.

(Rate of Viscosity Change) The pigment dispersion compositions for black matrices prepared in Examples and Comparative Examples were stored at 40° C. for one month. Before and after the above storage, use an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., R100 type viscometer type RE100L) to measure the viscosity at 25°C, and obtain the viscosity change rate [(viscosity after storage - viscosity before storage) / (viscosity before storage)], and evaluated by the following criteria. The results are shown in Table 1. ○: The viscosity change rate before and after storage is 10% or less. ×: The viscosity change rate before and after storage exceeded 10%.

化合物

化合物1 1.5 1.5 - - 1.5 1.5 1.5 1.5 1.5 1.5 -

化合物2 - - 1.5 - - - - - - - -

化合物3 - - - 1.5 - - - - - - - 有機溶劑 PM 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 PGMEA 66.9 66.9 66.9 66.9 66.9 66.9 66.9 67.5 68.1 66.9 68.4 合計 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 評價試驗 黏度（mPa・s） 5.1 5.3 5.0 5.0 5.0 5.0 5.5 8.0 5.0 5.7 5.0 黏度變化 ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○ [Table 1] Pigment dispersion composition for black matrix Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 black colorant Carbon Black 1 20.0 20.0 20.0 20.0 20.0 20.0 - 20.0 20.0 20.0 20.0 Carbon Black 2 - - - - - - 20.0 - - - - Pigment Dispersant Pigment dispersant 1 (40% solid content) 5.0 - 5.0 5.0 5.0 5.0 5.0 5.0 - - 5.0 Pigment dispersant 2 (40% solid content) - 5.0 - - - - - - - - - Pigment dispersant 3 (40% solid content) - - - - - - - - 3.8 - - Pigment dispersant 4 (solid content 52%) - - - - - - - - - 5.0 - Pigment Dispersing Auxiliary Pigment Dispersing Auxiliary 1 0.6 0.6 0.6 0.6 - - 0.6 - 0.6 0.6 0.6 Pigment Dispersing Auxiliary 2 - - - - 0.6 - - - - - - Pigment Dispersing Auxiliary 3 - - - - - 0.6 - - - - -

compound

Compound 1 1.5 1.5 - - 1.5 1.5 1.5 1.5 1.5 1.5 -

Compound 2 - - 1.5 - - - - - - - -

Compound 3 - - - 1.5 - - - - - - - Organic solvents PM 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 PGMEA 66.9 66.9 66.9 66.9 66.9 66.9 66.9 67.5 68.1 66.9 68.4 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Evaluation test Viscosity (mPa・s) 5.1 5.3 5.0 5.0 5.0 5.0 5.5 8.0 5.0 5.7 5.0 Viscosity change ○ ○ ○ ○ ○ ○ ○ × ○ ○ ○

Using a high-speed mixer, the above-mentioned pigment dispersion composition for black matrix and other materials (photopolymerizable compound, alkali-soluble resin, photopolymerization initiator, and organic solvent) were uniformly mixed so as to have the composition shown in Table 2. Filtered with a 3 μm filter to obtain photoresist compositions for black matrices of Examples and Comparative Examples.

<Evaluation test> (surface resistance value) The pigment-dispersed photoresist compositions for black matrices of Examples and Comparative Examples were coated on a glass substrate (Corning 1737) with a spin coater so that the film thickness was 1 μm, and pre-baked at 100° C. for 3 minutes. After that, exposure was performed with a high-pressure mercury lamp, and post-baking was performed at 230° C. for 3 hours to form a black photoresist pattern formed only on a solid portion. Using the main body: micro current meter R8340, optional parts: shielding box R12702A (both manufactured by Advance Company), the surface resistance value of each black photoresist pattern produced was measured. The results are shown in Table 2.

(developer solubility) The pigment-dispersed photoresist compositions for black matrices of Examples and Comparative Examples were coated on a glass substrate (Corning 1737) with a spin coater so that the film thickness was 1 μm, and pre-baked at 100° C. for 3 minutes. Then, it was made to immerse in the developing solution (0.05 mass % aqueous solution of potassium hydroxide) of 23 degreeC, and the melt|dissolution state was evaluated visually. The results are shown in Table 2.

(Developability) The pigment-dispersed photoresist compositions for black matrices of Examples and Comparative Examples were coated on a glass substrate (Corning 1737) with a spin coater so that the film thickness would be 1 μm, and the results were carried out at 100° C. 3 minutes pre-bake. Next, using a mask having line patterns of 5 μm, 8 μm, 10 μm, 15 μm, 20 μm, and 30 μm, exposure was performed ^{with a high-pressure mercury lamp with a cumulative UV light amount of 400 mJ/cm 2 .} Then, it was immersed in a developing solution (a 0.05 mass % aqueous solution of potassium hydroxide) at 23° C., and the time (break point) at which the developed pattern began to appear under a spray developing pressure of ^{0.5 kgf/cm 2 was measured, using the following criteria} Evaluate. The results are shown in Table 2. ○: The photoresist composition for black matrix in the mask portion can be completely removed within 30 seconds. △: The photoresist composition for black matrix of the mask part can be completely removed in more than 30 seconds and within 60 seconds. ×: The photoresist composition for black matrix in the mask portion could not be completely removed even if it exceeded 60 seconds.

[Table 2] Pigment-dispersed photoresist composition for black matrix Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pigment dispersion composition for black matrix Example 1 63.6 - - - - - - - - - - Example 2 - 63.6 - - - - - - - - - Example 3 - - 63.6 - - - - - - - - Example 4 - - - 63.6 - - - - - - - Example 5 - - - - 63.6 - - - - - - Example 6 - - - - - 63.6 - - - - - Example 7 - - - - - - 63.6 - - - - Example 8 - - - - - - 63.6 - - - Comparative Example 1 - - - - - - - - 63.6 - - Comparative Example 2 - - - - - - - - - 63.6 - Comparative Example 3 - - - - - - - - - - 63.6 photopolymerization initiator OXE02 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 photopolymerizable compound DPHA 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 Alkali Soluble Resin WR-301 (45% solid content) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Organic solvents PGMEA 24.4 24.4 24.4 24.4 24.4 24.4 24.4 24.4 24.4 24.4 23.4 total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Evaluation results Surface resistance value (Ω/□) 3.8×10 ¹¹ 2.2×10 ¹¹ 7.6×10 ¹¹ 2.8×10 ¹¹ 5.5×10 ¹² 6.6×10 ¹¹ 0.8×10 ¹⁰ 0.8×10 ¹¹ 6.8×10 ¹² 3.6×10 ⁸ 2.6×10 ⁸ Developer Solubility dissolve dissolve dissolve dissolve dissolve dissolve dissolve dissolve peel off dissolve dissolve developability ○ ○ ○ ○ ○ △ △ △ × ○ ○

化合物、及有機溶劑，且上述顏料分散劑為含有氮原子之丙烯酸系嵌段共聚物之黑矩陣用顏料分散組成物，可形成黑矩陣用光阻組成物之顯影性優異、且即使進行高溫且長時間之後烘烤，表面電阻值亦優異之黑矩陣。 另一方面，確認到，未使用碳二亞胺系之顏料分散劑之比較例1，顯影液溶解性差（無法溶解，而且剝離）、顯影性亦差。又，使用胺酯系顏料分散劑之比較例2、及未使用

化合物之比較例3，進行了高溫且長時間之後烘烤時的表面電阻値不足。 [產業上之可利用性]According to the examples, it was confirmed that by using a black colorant, a pigment dispersant,

A compound, an organic solvent, and the above-mentioned pigment dispersant is a pigment dispersion composition for a black matrix of an acrylic block copolymer containing a nitrogen atom, which can form a photoresist composition for a black matrix. A black matrix with excellent surface resistance after baking for a long time. On the other hand, it was confirmed that Comparative Example 1 in which a carbodiimide-based pigment dispersant was not used was poor in developer solubility (insoluble and peeled off) and poor in developability. Moreover, the comparative example 2 which used the urethane type pigment dispersant, and did not use

In Comparative Example 3 of the compound, the surface resistance value at the time of baking at a high temperature for a long time was insufficient. [Industrial Availability]

ADVANTAGE OF THE INVENTION According to this invention, the pigment dispersion composition for black matrices which can form the black matrix which is excellent in the developability of the photoresist composition for black matrices, and is excellent in surface resistance value even if it bakes after a high temperature and a long time can be provided.

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Claims (8)

A pigment dispersion composition for a black matrix, comprising: a black colorant, a pigment dispersant,

Compound, and organic solvent; The above-mentioned pigment dispersant is a nitrogen atom-containing acrylic block copolymer. The pigment dispersion composition for a black matrix according to claim 1, further comprising a pigment dispersion auxiliary. The pigment dispersion composition for a black matrix according to claim 2, wherein the pigment dispersion aid is a phthalocyanine compound. The pigment dispersion composition for a black matrix according to any one of claims 1 to 3, wherein the above

The compound is a compound represented by the following general formula (1) and/or (2),

[In the general formula (1), R ¹ and R ² represent an alkyl group or an aryl group which may have an unsaturated bond, which may be the same or different from each other, and X ¹ is a divalent linking group; In the general formula (2), R ³ and R ⁴ represents an alkyl group or an aryl group which may have an unsaturated bond, which may be the same or different from each other, and X ² is a divalent linking group]. The pigment dispersion composition for a black matrix according to any one of claims 1 to 4, wherein the black colorant contains carbon black. The pigment dispersion composition for a black matrix according to claim 5, wherein the carbon black is acid carbon black. A photoresist composition for a black matrix obtained from the pigment dispersion composition for a black matrix according to any one of claims 1 to 6. A black matrix formed from the photoresist composition for a black matrix of claim 7.