JPWO2016098804A1 - Colored curable resin composition - Google Patents

Abstract

It is an object of the present invention to provide a colored curable resin composition excellent in light-shielding property and pattern forming property, a color filter including a black matrix formed using the same, and a dispersion. [1] A compound (A1) represented by the following formula (1), aniline black (A2), a dispersant (B), an organic solvent (C), and a curable compound (D), A colored curable resin composition having a mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) of 0.10 or more and 0.50 or less, [2] [3] a color filter comprising a black matrix formed using the colored curable resin composition according to [1], [3] a compound (A1) represented by the following formula (1), and aniline black (A2) And a dispersant (B) and an organic solvent (C), and the mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) is 0.00. Dispersion which is 10 or more and 0.50 or less.

Description

  The present invention relates to a color curable resin composition used for producing a color filter used in a color liquid crystal display device, a color image pickup tube element, and the like, a color filter including a black matrix formed using the same, and a dispersion It is about the body.

A grid-like black pattern called a black matrix (hereinafter also referred to as “BM”) having a light shielding property is formed in the gaps between the red, green, and blue filter segments of the color filter for the purpose of improving contrast. It is common.
The BM is required to have excellent light shielding properties in order to improve the image quality of the liquid crystal display. In particular, in order to cope with higher definition and higher brightness in recent years, a BM is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device from a conventional method of forming a BM on a color filter substrate. The BOA (Black Matrix on Array) method has been studied. This BOA method eliminates the need for a pasting process for aligning with the element, greatly increases the pixel aperture ratio (aperture ratio), and shortens the manufacturing process. Since the quality can be improved and the cost can be reduced, there are many advantages over the conventional method of forming a BM on a color filter substrate.

However, when a BM is to be formed on the array substrate side, the BM itself is in direct contact with the liquid crystal. Therefore, if the insulation of the BM itself is low, a display failure of the liquid crystal display is caused.
Moreover, since the mask alignment performed at the time of BM formation is performed using an infrared camera, a certain level of light transmittance in the near infrared region is also required. Therefore, carbon black, which has been mainly used as a conventional BM material, not only exhibits a high dielectric constant and poor insulation, but also has a low light transmittance in the near infrared region, making alignment difficult. It is difficult to use for a BOA type liquid crystal panel.
As a method for solving such a problem, a method of providing light shielding properties with a specific organic pigment (see Patent Document 1) is disclosed.

Special table 2012-515233 gazette

〔式（１）中、Ｘは二重結合を示し、幾何異性体としてそれぞれ独立にＥ体又はＺ体であり、Ｒ^１は、各々独立に、水素原子、メチル基、ニトロ基、メトキシ基、臭素原子、塩素原子、フッ素原子、カルボキシ基、又はスルホン酸基を示し、Ｒ^２は、各々独立に、水素原子、メチル基、又はフェニル基を示し、Ｒ^３は、各々独立に、水素原子、メチル基、又は塩素原子を示す。〕
〔２〕 〔１〕に記載の着色硬化性樹脂組成物を用いて形成されるブラックマトリクスを具備する、カラーフィルタ。
〔３〕 式（１）で表される化合物（Ａ１）と、アニリンブラック（Ａ２）と、分散剤（Ｂ）と、有機溶媒（Ｃ）と、を含有し、化合物（Ａ１）とアニリンブラック（Ａ２）との合計に対する化合物（Ａ１）の質量比［Ａ１／（Ａ１＋Ａ２）］が０．１０以上０．５０以下である分散体。The present invention relates to the following [1] to [3].
[1] A compound (A1) represented by the formula (1), aniline black (A2), a dispersant (B), an organic solvent (C), and a curable compound (D), A colored curable resin composition having a mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) of 0.10 or more and 0.50 or less.

[In the formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, Each represents a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom, A methyl group or a chlorine atom is shown. ]
[2] A color filter comprising a black matrix formed using the colored curable resin composition according to [1].
[3] A compound (A1) represented by formula (1), aniline black (A2), a dispersant (B), and an organic solvent (C) are contained, and compound (A1) and aniline black ( Dispersion whose mass ratio [A1 / (A1 + A2)] of compound (A1) with respect to the sum total with A2) is 0.10 or more and 0.50 or less.

In general, a BM of a color filter is formed on a substrate by a photolithography method. However, the composition disclosed in Patent Document 1 is not sufficient in terms of pattern formation in a photolithography process. Therefore, it is desired to provide a colored curable resin composition for BM that is excellent in light shielding properties and pattern formability.
An object of the present invention is to provide a colored curable resin composition excellent in light-shielding properties and pattern-forming properties, a color filter including a black matrix formed using the same, and a dispersion.

〔式（１）中、Ｘは二重結合を示し、幾何異性体としてそれぞれ独立にＥ体又はＺ体であり、Ｒ^１は、各々独立に、水素原子、メチル基、ニトロ基、メトキシ基、臭素原子、塩素原子、フッ素原子、カルボキシ基、又はスルホン酸基を示し、Ｒ^２は、各々独立に、水素原子、メチル基、又はフェニル基を示し、Ｒ^３は、各々独立に、水素原子、メチル基、又は塩素原子を示す。〕
〔２〕 〔１〕に記載の着色硬化性樹脂組成物を用いて形成されるブラックマトリクスを具備する、カラーフィルタ。
〔３〕 式（１）で表される化合物（Ａ１）と、アニリンブラック（Ａ２）と、分散剤（Ｂ）と、有機溶媒（Ｃ）と、を含有し、化合物（Ａ１）とアニリンブラック（Ａ２）との合計に対する化合物（Ａ１）の質量比［Ａ１／（Ａ１＋Ａ２）］が０．１０以上０．５０以下である分散体。The present inventors include a colored curable resin composition having excellent light-shielding properties and pattern-forming properties by containing the compound (A1) of formula (1) and aniline black (A2) at a specific mass ratio as a black color material. It was found that a product was obtained.
That is, the present invention relates to the following [1] to [3].
[1] A compound (A1) represented by the formula (1), aniline black (A2), a dispersant (B), an organic solvent (C), and a curable compound (D), A colored curable resin composition having a mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) of 0.10 or more and 0.50 or less.

[In the formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, Each represents a bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom, A methyl group or a chlorine atom is shown. ]
[2] A color filter comprising a black matrix formed using the colored curable resin composition according to [1].
[3] A compound (A1) represented by formula (1), aniline black (A2), a dispersant (B), and an organic solvent (C) are contained, and compound (A1) and aniline black ( Dispersion whose mass ratio [A1 / (A1 + A2)] of compound (A1) with respect to the sum total with A2) is 0.10 or more and 0.50 or less.

  According to the present invention, it is possible to provide a colored curable resin composition excellent in light-shielding properties and pattern-forming properties, a color filter including a black matrix formed using the same, and a dispersion.

The colored curable resin composition of the present invention (hereinafter also simply referred to as “resin composition”) includes a compound (A1) represented by formula (1) (hereinafter also referred to as “compound (A1)”), aniline black, and (A2), a dispersing agent (B), an organic solvent (C), and a curable compound (D) are contained.
In the resin composition of the present invention, the mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) is 0.10 from the viewpoints of light shielding properties and pattern forming properties. It is 0.50 or less.
According to the present invention, by using the compound (A1) and aniline black (A2) in combination, a resin composition that exhibits a synergistic effect and is excellent in light-shielding properties and pattern-forming properties can be obtained.

[Colored curable resin composition]
[Black color material]
<Compound (A1)>
The resin composition of this invention contains the compound (A1) and aniline black (A2) represented by Formula (1) from a viewpoint of light-shielding property and pattern formation property as a black color material.

In formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, or bromine. An atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfo group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom, a methyl group, or Or a chlorine atom.
The compound represented by Formula (1) can be used individually or in combination of 2 or more types.
From the viewpoint of ease of production of the compound (A1), R ¹ is preferably bonded to the 6-position of the dihydroindolone ring, and R ³ is preferably bonded to the 4-position of the dihydroindolone ring. From the same viewpoint, R ¹ , R ² and R ³ are preferably hydrogen atoms.
Compound (A1) has EE, ZZ, and EZ isomers as geometric isomers. The compound used in the present invention may be any one of these compounds, or these geometric isomers. It may be a mixture of

  The said compound (A1) can be manufactured by the method described in international publication WO2000 / 24736, international publication WO2010 / 081624, for example. Examples of the commercially available compound (A1) include “Irgaphor Black S0100CF” manufactured by BASF.

<Aniline Black (A2)>
Aniline black is a black powder pigment produced by oxidative condensation of aniline, and is an oxidative condensation mixture of aniline derivatives and the like. Depending on the reaction conditions of the oxidative condensation, it becomes a mixture with several kinds of intermediates and by-products.

The average particle diameter of aniline black (A2) in the present invention is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.24 μm or more, and further preferably 0.27 μm or more, from the viewpoint of light shielding properties. More preferably, it is 0.30 μm or more, more preferably 0.35 μm or more. From the viewpoint of pattern formation, it is preferably 1.5 μm or less, more preferably 1.0 μm or less, still more preferably 0.7 μm or less, Preferably it is 0.5 micrometer or less. The measuring method of the average particle diameter of aniline black is based on the method described in the examples.
The BET specific surface area of aniline black (A2) in the present invention is preferably 34 m ² / g or less, more preferably 17 m ² / g or less, still more preferably 14 m ² / g or less, and further preferably 12 m from the viewpoint of light shielding properties. ² / g or less, more preferably 11 m ² / g or less, and from the viewpoint of pattern formability, preferably 2.2 m ² / g or more, more preferably 3.3 m ² / g or more, and still more preferably 4.7 m. ^{It is 2} / g or more, more preferably 6.6 m ² / g or more. The method for measuring the BET specific surface area of aniline black is according to the method described in the examples.

The aniline black (A2) in the present invention is preferably chromium-free from the viewpoint of safety. Chromium-free aniline black can be manufactured by the method described in international publication WO2012 / 099203, international publication WO2012 / 099204, for example.
Examples of commercially available aniline black include “Toshiki 5030 conc”, “No. 2 Super Black”, “No. 2 aniline black”, “No. 25 aniline black” manufactured by Tokyo Color Materials Co., Ltd., manufactured by Toda Industry Co., Ltd. "NAB1101", "Diamond Black S" manufactured by Noma Chemical Co., Ltd., "Diamond Black S" manufactured by Daito Kasei Co., Ltd., "B", "BX", "XBE" of "Monolite Black" series manufactured by ICI -HD "," Diamond Black # 300 "manufactured by BASF," Segnar Light Black SNT "," Turmo Solid Supra Black SNT "," Pigment Black A "," Pariotol Black "series" D0080 "," K0080 "," L0080 "and the like.

  The resin composition of the present invention may contain a black color material other than the compound (A1) and aniline black (A2) as long as the effects of the present invention are not impaired. Examples of other black color materials include carbon black and titanium black. In this specification, the compound (A1), aniline black (A2) and other black color materials are collectively referred to as “black color material (A)”.

In the resin composition of the present invention, the mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) is 0.10 or more from the viewpoint of light shielding properties and viewpoints. , Preferably 0.15 or more, more preferably 0.20 or more, still more preferably 0.24 or more, still more preferably 0.28 or more, and from the viewpoint of pattern formability, 0.50 or less, preferably 0.40 or less, more preferably 0.35 or less, and still more preferably 0.32 or less.
The mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) is preferably 0.28 or less, more preferably from the viewpoint of obtaining remarkable pattern forming properties. It is 0.26 or less, more preferably 0.25 or less.
In the black color material (A) contained in the resin composition of the present invention, the total amount of the compound (A1) and aniline black (A2) is preferably 80% by mass or more, more preferably 90% by mass or more, It is 100 mass% or less, More preferably, it is 100 mass%.
From the viewpoint of increasing the affinity between the black color material and the organic solvent, and improving the dispersibility and storage stability, the black color material may be a resin or polymer on the surface of the compound (A1) or aniline black (A2). The thing which surface-treated beforehand with the derivative | guide_body etc. of the said compound (A1) or aniline black (A2) can also be used.

[Dispersant (B)]
Examples of the dispersant include, for example, a polyurethane-based dispersant, a polyamide-based dispersant, a polyimide-based dispersant, poly (meth) acrylic acid having poly (meth) acrylate, polylactone, polyalkylene oxide or the like as a main chain or a side chain. Examples thereof include polycarboxylic acid-based dispersants such as poly (anhydride) maleic acid, polyamine-based dispersants, and dispersants in which a quaternary ammonium salt or the like is introduced into a part thereof. These dispersants can be used alone or in admixture of two or more.
The dispersant is preferably a dispersant obtained by reacting a polyamine compound having 1 to 5 nitrogen atoms with a quaternizing agent having an average addition mole number of 1 to 100 and having a lactone chain or an alkyleneoxy chain ( B1).

  Examples of commercially available dispersants include “Disperbyk” series “161”, “166”, “167” manufactured by Big Chemie Japan Co., Ltd., “Solsperse” series “55000”, “76500” manufactured by Nippon Lubrizol Co., Ltd. Polyurethane dispersants: “Disperbyk” series “106”, “110”, “111” manufactured by Big Chemie Japan Co., Ltd. “Solsperse” series “36000”, “41000” manufactured by Nippon Lubrizol Co., Ltd., BASF Japan Ltd. Polycarboxylic acid-based dispersants such as “EFKA-5060” manufactured by the company; “116” and “130” of “Disperbyk” series manufactured by Big Chemie Japan Co., Ltd. “24000” of “Solspers” series manufactured by Nippon Lubrizol Co., Ltd. "32000" Polyamines such as “33000”, “J200”, “EFKA-4046” manufactured by BASF Japan Ltd., “821”, “822”, “824”, “881”, etc. of “Ajisper PB” series manufactured by Ajinomoto Fine Techno Co. A dispersing agent is mentioned. Among these, from the viewpoint of dispersibility, it is preferably a polyamine dispersant, more preferably at least one selected from “EFKA-4046” and “Solspers J200”, and more preferably “Solspers J200”.

<Dispersant (B1)>
The dispersant (B1) is preferably obtained by reacting a polyamine compound having 1 to 5 nitrogen atoms with a quaternizing agent having an lactone chain having an average addition mole number of 1 to 100 or an alkyleneoxy chain. For example, the dispersant is a reaction product of a polyamine compound having 1 to 5 nitrogen atoms and a quaternizing agent having an alkyleneoxy chain having an average addition mole number of 1 to 100.
The equivalent ratio of the quaternizing agent to the equivalent of the polyamine compound [quaternizing agent equivalent / polyamine equivalent] is preferably 0.3 or more, more preferably 0.6 or more. From the viewpoint of property, it is 1.0 or less, preferably 0.9 or less.

  The number of nitrogen atoms in the polyamine compound is preferably 1 or more, more preferably 2 or more, and preferably 4 or less, more preferably 3 from the viewpoints of increasing dispersibility and improving the storage stability of the dispersion. And preferably 2.

〔式中、Ｒ_１、Ｒ_２、Ｒ_４は、同一又は異なっていてもよく、水素原子の一部が水酸基で置換されていてもよい炭素数１以上１０以下の炭化水素基を示し、Ｒ_５は炭素数１以上１８以下のアルカンジイル基（ただしＲ_１と隣接しているＲ_５は単結合を示す）を示し、ｎ１は平均構造単位数を示し、ｎ１は１以上５以下である。〕The polyamine compound is preferably a compound represented by the following formula (B1a).

[Wherein R ₁ , R ₂ and R ₄ may be the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms in which a part of hydrogen atoms may be substituted with a hydroxyl group; ₅ represents an alkanediyl group having 1 to 18 carbon atoms (where R ₅ adjacent to R ₁ represents a single bond), n1 represents the average number of structural units, and n1 is 1 to 5 inclusive. ]

R ₁ and R ₂ are preferably a hydrocarbon group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms, a hydrocarbon group having 1 to 5 carbon atoms, or 3 to 6 carbon atoms. The hydroxyalkyl group is more preferably a hydrocarbon group having 1 to 3 carbon atoms or a hydroxyalkyl group having 4 to 6 carbon atoms.
The carbon number of R ₄ is preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, and still more preferably 1. R ₄ is preferably a hydrocarbon group not substituted with a hydroxyl group. Specific examples of R ₄ include at least one selected from a methyl group, an ethyl group, a butyl group, a hexyl group, a hydroxymethyl group, a hydroxybutyl group, and a hydroxyhexyl group, and preferably a methyl group And at least one selected from ethyl groups, more preferably methyl groups.

The carbon number of the alkanediyl group of R ₅ is 1 or more from the viewpoint of improving the pigment dispersibility, preferably 2 or more, more preferably 3 or more from the viewpoint of improving the pigment dispersibility. From the viewpoint, it is 18 or less, preferably 14 or less, more preferably 12 or less, still more preferably 10 or less, and still more preferably 6 or less.
Examples of the alkanediyl group of R ₅ include at least one selected from a methylene group, an ethylene group, various propanediyl groups, various hexanediyl groups, various octanediyl groups, and various nonanediyl groups. From the viewpoint, it is preferably at least one selected from a propane-1,3-diyl group, a hexane-1,6-diyl group, and a nonane-1,9-diyl group, and from the viewpoint of improving pigment dispersibility, Preferably at least one selected from a propane-1,3-diyl group and a hexane-1,6-diyl group, more preferably a hexane-1,6-diyl group.
Examples of the polyamine compound include N, N, N ′, N′-tetramethylhexanediamine, N, N, N ′, N′-tetramethylpropanediamine, and polyamine glycol having 2 to 4 nitrogen atoms.

The polyamine compound can be obtained, for example, by a method in which an alkylene diol and a primary amine or a secondary amine are reacted in the presence of a Cu-Ni catalyst, or a method in which an alkylene diamine is reductively alkylated with an aldehyde.
In addition, as commercially available products, N, N, N ′, N′-tetramethylhexanediamine (“Kaorizer No. 1” manufactured by Kao Corporation), N, N, N ′, N′-tetramethylpropanediamine (Kao) “Kaorraiser No. 2” manufactured by Co., Ltd.), polyamine glycol (“Kaorraiser P200” manufactured by Kao Corporation) and the like can be used.

  Examples of the quaternizing agent include halogenated alkyl ester compounds having a lactone chain having an average addition mole number of 1 or more and 100 or less, or an alkyleneoxy chain.

The lactone chain is preferably, for example, a ring-opening polymer of lactone. Examples of the lactone include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. These can be used alone or in combination of two or more. In addition, when multiple types of lactones are used, the arrangement may be random or block.
Of these lactones, ε-caprolactone is preferred.
The average number of added moles of the polyester chain is 2 or more from the viewpoint of improving the dispersibility and storage stability of the dispersion, the developability of the coloring composition, and the heat resistance, and preferably 10 or more. Preferably, it is 15 or more, and from the same viewpoint, it is 100 or less, preferably 70 or less, more preferably 50 or less.

The number of carbon atoms in the alkyleneoxy unit is preferably 2 or more, and is preferably 4 or less, more preferably 3 or less.
The alkyleneoxy chain is preferably a structural unit represented by the following formula (B1b) from the viewpoint of improving pigment dispersibility.

〔式（Ｂ１ｂ）中、ＰＯはプロピレンオキシド由来の単位を示し、ＥＯはエチレンオキシド由来の単位を示し、ｂ，ｃは平均付加モル数を示し、ｂは０〜１００であり、ｃは０〜１００であり、ｂ＋ｃは１〜１００である。＊は結合部位を示す。〕
上記式（Ｂ１ｂ）は、該構造単位がブロック重合体であることが好ましく、上記式（Ｂ１ｂ）の（ＰＯ）末端側はアルコキシ基と結合し、（ＥＯ）末端側はハロゲン化アルキルエステルに結合することが好ましい。

[In the formula (B1b), PO represents a unit derived from propylene oxide, EO represents a unit derived from ethylene oxide, b and c represent the average number of added moles, b is 0 to 100, and c is 0 to 100. And b + c is 1 to 100. * Indicates a binding site. ]
In the formula (B1b), the structural unit is preferably a block polymer, the (PO) terminal side of the formula (B1b) is bonded to an alkoxy group, and the (EO) terminal side is bonded to a halogenated alkyl ester. It is preferable to do.

The average added mole number b is preferably 10 or more, more preferably 21 or more, and still more preferably 25 or more, from the viewpoint of improving pigment dispersibility and fixability of the exposed portion. From the viewpoint of ease of production of B1), it is preferably 60 or less, more preferably 50 or less, and still more preferably 35 or less.
The average added mole number c is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, from the viewpoint of improving pigment dispersibility and solubility of the non-exposed area, and from the viewpoint of fixing properties of the exposed area. Preferably it is 95 or less, More preferably, it is 70 or less, More preferably, it is 50 or less, More preferably, it is 30 or less, More preferably, it is 20 or less.
The total of b and c (b + c) is preferably 15 or more, more preferably 21 or more, still more preferably 30 or more, still more preferably 40 or more, preferably 95 or less, from the viewpoint of improving pigment dispersibility. More preferably, it is 70 or less, More preferably, it is 50 or less.
The ratio of b to the total of b and c (b / (b + c)) is preferably 0.2 or more, more preferably 0.4 or more, and still more preferably, from the viewpoint of improving pigment dispersibility and fixability of the exposed portion. Is 0.5 or more, and preferably 0.97 or less, more preferably 0.86 or less, and still more preferably 0.8 or less, from the viewpoint of the solubility of the non-exposed area and the ease of production of the dispersant (B1). It is.

The alkyleneoxy chain is preferably an alkoxyalkyleneoxy group.
The number of carbon atoms of the alkoxy group is 1 or more from the viewpoint of improving pigment dispersibility, preferably 6 or more, more preferably 10 or more, preferably 18 or less, more preferably 16 or less, still more preferably. 14 or less, more preferably 12 or less.
Examples of the alkoxy group include at least one selected from a methyl group, a decyl group, a lauryl group, an oleyl group, a stearyl group, a p-octylphenyl group, and a p-nonylphenyl group. The alkoxy group is preferably an aliphatic hydrocarbon group from the viewpoint of improving pigment dispersibility, more preferably at least one selected from a methyl group, a decyl group, and a lauryl group, and more preferably a lauryl group. .

〔式中、Ｒ_６は炭素数１以上４以下のアルカンジイル基を示し、Ｒ_７１は炭素数２以上１２以下のアルカンジイル基を示し、ａは平均付加モル数を示し、１以上１００以下であり、Ｒ_８Ｏはアルコキシ基を示し、Ｙ_１は脱離基を示す。〕

〔式中、Ｒ_６は炭素数１以上４以下のアルカンジイル基を示し、Ｒ_７２Ｏは炭素数２以上４以下のアルキレンオキシド基を示し、ａは平均付加モル数を示し、１以上１００以下であり、Ｒ_８Ｏはアルコキシ基を示し、Ｙ_１は脱離基を示す。〕
Ｙ_１は、分散剤の製造容易性、並びに分散体の分散性及び保存安定性を向上させる観点から、好ましくは、ハロゲン原子、アルキル硫酸基、アルキルベンゼンスルホニル基、及びアルキルカーボネート基から選ばれる１種、より好ましくはハロゲン原子、更に好ましくは、塩素原子、臭素原子、及びヨウ素原子から選ばれる少なくとも１種、更に好ましくは塩素原子である。The quaternizing agent is preferably a compound represented by the following formula (B1c-1) or formula (B1c-2).

[In the formula, R ₆ represents an alkanediyl group having 1 to 4 carbon atoms, R ₇₁ represents an alkanediyl group having 2 to 12 carbon atoms, a represents an average added mole number, and 1 to 100 inclusive. Yes, R ₈ O represents an alkoxy group, and Y ₁ represents a leaving group. ]

[In the formula, R ₆ represents an alkanediyl group having 1 to 4 carbon atoms, R ₇₂ O represents an alkylene oxide group having 2 to 4 carbon atoms, a represents an average added mole number, and 1 to 100 inclusive. R ₈ O represents an alkoxy group, and Y ₁ represents a leaving group. ]
Y ₁ is preferably one kind selected from a halogen atom, an alkyl sulfate group, an alkylbenzenesulfonyl group, and an alkyl carbonate group from the viewpoint of improving the ease of production of the dispersant and the dispersibility and storage stability of the dispersion. More preferably a halogen atom, still more preferably at least one selected from a chlorine atom, a bromine atom and an iodine atom, still more preferably a chlorine atom.

From the viewpoint of improving the dispersibility and storage stability of the dispersion, R _{71 has} a carbon number of 2 or more, preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more, from the same viewpoint. , 12 or less, preferably 10 or less, more preferably 7 or less, still more preferably 6 or less, and still more preferably 5 or less.
Examples of R ₇₁ include at least one selected from an ethylene group, various propanediyl groups, various butanediyl groups, various pentanediyl groups, various hexanediyl groups, and various heptanediyl groups. Dispersibility and storage stability of the dispersion From the viewpoint of improving the properties, a pentane-1,5-diyl group is preferable.

The number of carbon atoms of R ₇₂ is preferably 4 or less, more preferably 3 or less, and preferably 2 or more, from the viewpoints of dispersibility and storage stability. R ₇₂ is preferably at least one selected from an ethylene group and a propylene group.

  a is 2 or more from the viewpoint of improving the dispersibility and storage stability of the dispersion, preferably 10 or more, more preferably 15 or more, and from the same viewpoint, 100 or less, preferably 70 or less. More preferably, it is 50 or less.

The number of carbon atoms of R ₆ is 4 or less, preferably 3 or less, more preferably 2 or less, and preferably 1 or more, more preferably, from the viewpoint of ease of production of the dispersant of the present invention. 1. R ₆ is preferably a methylene group.

The carbon number of R ₈ is 1 or more from the viewpoint of improving the dispersibility and storage stability of the dispersion, preferably 6 or more, more preferably 10 or more, and 18 or less from the same viewpoint, Preferably it is 16 or less, More preferably, it is 14 or less. R ₈ is preferably at least one selected from an aliphatic hydrocarbon group and a hydrocarbon group having an aromatic ring, more preferably an aliphatic hydrocarbon group, from the viewpoint of improving the dispersibility and storage stability of the dispersion. More preferred is at least one selected from an alkyl group and an alkenyl group, and more preferred is an alkyl group.
Examples of R ₈ include methyl, ethyl, octyl, decyl, lauryl, myristyl, cetyl, oleyl, stearyl, phenyl, p-octylphenyl, and p-nonylphenyl. There may be mentioned at least one selected, and a lauryl group is preferable from the viewpoint of improving the dispersibility and storage stability of the dispersion.

  The dispersant (B1) may have a structural unit derived from a quaternizing agent other than the above.

Other quaternizing agents include hydrocarbon compounds having a leaving group and having 1 to 10 carbon atoms. From the viewpoint of improving the dispersibility and storage stability of the dispersion, the number of carbon atoms of the hydrocarbon compound is 10 or less, preferably 7 or less, more preferably 4 or less, still more preferably 2 or less, and 1 That's it.
Examples of the hydrocarbon compound having a leaving group include at least one selected from dialkyl sulfate, alkyl halide, and alkyl p-toluenesulfonate. Specific examples include dimethyl sulfate, diethyl sulfate, dipropyl sulfate, bromide. Examples include methane, ethane bromide, propane bromide, methane iodide, ethane iodide, and propane iodide.
The dispersant (B1) may be neutralized with an acid.

  The weight average molecular weight of the dispersant (B1) is preferably 2,000 or more, more preferably 3,000 or more, and further preferably 3,500 or more, from the viewpoints of dispersibility, storage stability, and redispersibility. Moreover, Preferably it is 35,000 or less, More preferably, it is 20,000 or less, More preferably, it is 10,000 or less. The measuring method of a weight average molecular weight is based on the method as described in an Example.

<Method for producing dispersant (B1)>
The dispersant (B1) can be obtained by reacting a polyamine compound having 1 to 5 nitrogen atoms with a quaternizing agent. The reaction atmosphere in the reaction for obtaining the dispersant (B1) is preferably an inert gas atmosphere such as a nitrogen gas atmosphere or argon. The reaction temperature in this step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, and preferably 100 ° C. or lower.

[Organic solvent (C)]
Examples of the organic solvent include monohydric alcohols such as ethanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane; Alcohol; ethers such as ethylene glycol diethyl ether, ethyl acetate, silicone oil, fats and oils, and a compound represented by the following formula (SL1).

In formula (SL1), R ⁴ and R ⁵ are each independently a straight or branched chain having 1 to 4 carbon atoms in which hydrogen may be substituted with an alkoxy group having 1 to 3 carbon atoms. An alkyl group, R ⁶ represents a hydrogen atom or a methyl group, and n represents an integer of 0 or more and 3 or less.

In the formula (SL1), R ⁴ and R ⁵ are methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methoxybutyl, isobutyl, sec-butyl, and tert- A butyl group is mentioned, Preferably it is at least 1 sort (s) chosen from a methyl group and an ethyl group.
n is preferably 1 or 2.
The organic solvent is preferably ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), diethylene glycol monomono from the viewpoint of the dispersibility of the coloring material and the solubility or dispersibility of the dispersant. At least one selected from the group consisting of butyl ether acetate, 3-methoxybutyl acetate and propylene glycol monoethyl ether acetate, more preferably PGMEA.
Said organic solvent can be used individually or in combination of 2 or more types.

[Curable compound (D)]
Examples of the curable compound include polyfunctional polymerizable compounds.
<Polyfunctional polymerizable compound>
The polyfunctional polymerizable compound has two or more ethylenically unsaturated bonds.
Examples of the site having an ethylenically unsaturated bond include a (meth) acrylate group and a vinyl group.
A polyfunctional (meth) acrylate compound is preferably used as the polyfunctional polymerizable compound.
From the viewpoint of pattern formation, the number of ethylenically unsaturated bonds contained in the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 8 Or less, more preferably 7 or less, and even more preferably 6 or less.

As this polyfunctional (meth) acrylate compound, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hex (Meth) acrylate, pentaerythritol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, Glycerin tri (meth) acrylate, glycerin polyglycidyl ether poly (meth) acrylate, reaction product of polyisocyanate and hydroxyalkyl (meth) acrylate (urethane (meth) acrylate), methylene vinyl (Meth) acrylamide, dimethylene ether bis (meth) acrylamide, a condensation product of a polyhydric alcohol and N- methylol (meth) acrylamide, triacrylformal and the like. These polyfunctional (meth) acrylate compounds can be used alone or in combination of two or more.
Among these, preferably trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate At least one selected from the group consisting of dipentaerythritol hexaacrylate (hereinafter also referred to as “DPHA”).
In this specification, “(meth) acrylate” means at least one selected from acrylate and methacrylate. “(Meth) acrylamide” means at least one selected from acrylamide and methacrylamide.
Examples of the curable compound may include monofunctional polymerizable compounds such as (meth) acrylic acid, (meth) acrylic acid ester having a hydrocarbon group having 1 to 18 carbon atoms, and vinyl acetate.

  The resin composition of the present invention may contain an alkali-soluble resin (E), a thiol compound, a fluorine compound, a photopolymerization initiator, a photoinitiation assistant, and the like.

[Alkali-soluble resin (E)]
The alkali-soluble resin is used for dissolving an unexposed portion in a developer when a color filter is produced by a photolithography method. As the alkali-soluble resin, those generally used for negative resists can be used, and those having solubility in an alkaline aqueous solution, that is, 1% by mass in a 0.05% by mass tetramethylammonium hydroxide aqueous solution at 20 ° C. What is necessary is just to melt | dissolve above.
As the alkali-soluble resin used in the present invention, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid is preferably used.
(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and Examples include at least one selected from benzyl (meth) acrylate, preferably at least one selected from benzyl (meth) acrylate and methyl (meth) acrylate. That is, the copolymer of (meth) acrylic acid ester and (meth) acrylic acid is more preferably a copolymer of benzyl (meth) acrylate and (meth) acrylic acid and methyl (meth) acrylate and (meta ) At least one selected from copolymers with acrylic acid.
The molar ratio ((meth) acrylic acid ester / (meth) acrylic acid) of (meth) acrylic acid ester and (meth) acrylic acid forming the copolymer is preferably 50/50 or more, more preferably 70. / 30 or more, preferably 90/10 or less, more preferably 80/20 or less.
The weight average molecular weight of the alkali-soluble resin is preferably 5,000 or more, more preferably 7,000 or more, preferably 50,000 or less, more preferably 30,000 or less.
In this specification, “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.

[Thiol compound]
Since BM is immersed in a solvent such as N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) that dissolves the polyimide precursor during polyimide film formation, BM is required to have solvent resistance. The resin composition of the present invention may contain a thiol compound from the viewpoint of solvent resistance. The thiol compound is preferably a polyvalent thiol compound.
The thiol compound preferably has three or more mercapto groups from the viewpoint of solvent resistance. Since the crosslink density is increased by having three or more mercapto groups, it is considered that swelling of the resin composition after curing, elution of the black color material, and the like by a solvent such as NMP can be further suppressed.

The number of mercapto groups possessed by the thiol compound is preferably 3 or more, more preferably 4 or more from the viewpoint of solvent resistance, and preferably 9 or less, more preferably 8 from the viewpoint of availability. Hereinafter, it is more preferably 7 or less, and still more preferably 6 or less.
Examples of the thiol compound include an aliphatic thiol compound, a thiol compound having a cyclic structure such as a heterocyclic ring or an aromatic ring, and an aliphatic thiol compound is preferable from the viewpoint of solvent resistance.
The thiol compound preferably has a structure derived from mercaptocarboxylic acid from the viewpoint of solvent resistance.

Examples of the aliphatic thiol compound include 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio). Propane, trimethylolpropane tris (2-mercaptoacetate), glycerin tris (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptoacetate), dipentaerythritol pentakis (2-mercaptoacetate), dipenta Erythritol hexakis (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropioate) Over g), trimethylolpropane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto butyrate), dipentaerythritol hexakis (3-mercapto butyrate), and the like.
Examples of the thiol compound having a heterocyclic ring include tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, tris [(3-mercaptobutyryloxy) -ethyl] isocyanurate, (1,3,5-tris ( 3-mercaptobutyryloxyethyl) -1,3,5-triasian-2,4,6 (1H, 3H, 5H) -trione), tris [(3-mercaptopropionyloxy) -methyl] isocyanurate, etc. Is mentioned.
As thiol compounds having an aromatic ring, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) Benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,3,5-tris (mercapto) And ethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,2,3,4-tetramercaptobenzene, and the like.

  Among the above thiol compounds, preferably pentaerythritol tetrakis (3-mercaptopropionate), tris (3-mercaptopropionic acid) trimethylolpropane, 1,3,5-tris (3-mercaptobutyryloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, dipentaerythritol hexakis (3-mercaptopropionate) and tris-[(3-mercaptopropionyloxy) -ethyl] -At least one selected from isocyanurates, more preferably at least one selected from pentaerythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate), More preferably pentaerythrito Tetrakis (3-mercaptopropionate).

[Fluorine compound]
The resin composition of the present invention may contain a fluorine compound from the viewpoint of solvent resistance. Examples of the fluorine compound include at least one selected from a surfactant having a fluorocarbon chain, a fluorine-based oligomer, and a compound having a fluorocarbon chain and an ethylenically unsaturated bond.
As surfactants having a fluorocarbon chain, “430” and “431” of “Florinato FC” series manufactured by Sumitomo 3M Limited, “F142D” and “F171” of “MegaFuck” series manufactured by DIC Corporation are commercially available. , “F172”, “F173”, “F177”, “F183”, “F554”, “R30”, “301”, “303”, “351” of “F-top EF” series manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd. , “352”, “S-381”, “S-382”, “SC-101”, “SC-105” of “Surflon” series manufactured by AGC Seimi Chemical Co., Ltd., “E5844” manufactured by Daikin Fine Chemical Laboratory, Inc. Etc.
As a fluorine-type oligomer, AGC Seimi Chemical Co., Ltd. "Surflon S-611", "Surflon S-651", etc. are mentioned as a commercial item.
Examples of the compound having a fluorocarbon chain and an ethylenically unsaturated bond include “Megafac RS-72-K”, “Megafac RS-75”, and “Megafac RS-76-E” manufactured by DIC Corporation.
From the viewpoint of solvent resistance, the fluorine compound is preferably a fluorine-based oligomer, and at least one selected from a compound having a fluorocarbon chain and an ethylenically unsaturated bond, more preferably a fluorocarbon chain and an ethylenically unsaturated bond. It is a compound that has. A fluorine-based oligomer is considered to have excellent solvent resistance because of its high molecular weight and low solubility of the fluorine compound in the solvent. Since the compound having a fluorocarbon chain and an ethylenically unsaturated bond is copolymerized with the curable compound (D) at the time of curing, it is considered that the cured film has better solvent resistance.
Among the fluorine-based oligomers, “Surflon S-611” and “Surflon S-651” are preferable. Among the compounds having a fluorocarbon chain and an ethylenically unsaturated bond, “Megafac RS-72-K”, “Megafac RS-75”, and “Megafac RS-76-E” are preferable.
The fluorine compound used in the present invention may be one type or a mixture of two or more types.

(Photopolymerization initiator)
As the photopolymerization initiator, a known polymerization initiator can be used. For example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone 2-hydroxy-2-methyl-1-phenyl-propan-1-one, iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate, 2- [2-oxo 2-phenylacetoxyethoxy] ethyl ester and 2- (2-hydroxyethoxy) ethyl ester, phenyl glycolate, Benzophenone, and the like are preferable. Examples of commercially available photopolymerization initiators include “OXE02”, “369”, “907”, “651”, “2959”, “184”, “250”, “250”, “IRGACURE” series manufactured by BASF Japan Ltd. 754 ”;“ DAFOCUR ”series“ MBF ”,“ BP ”,“ 1173 ”are preferable. These photopolymerization initiators can be used alone or in combination of two or more.

(Photoinitiator)
You may combine a photoinitiator adjuvant with this photoinitiator.
Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, Examples include 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiation assistants can be used alone or in combination of two or more.

[Each component amount]
The total content of the compound (A1) and aniline black (A2) in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass from the viewpoints of light shielding properties and productivity. From the viewpoint of dispersibility and solvent resistance, it is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, and further preferably 15%. It is below mass%.

  The content of the compound (A1) in the resin composition is preferably 0.3% by mass or more, more preferably 1.0% by mass or more, still more preferably 2.0% by mass or more, from the viewpoint of light shielding properties. Preferably it is 2.5 mass% or more, More preferably, it is 3.0 mass% or more, More preferably, it is 4.0 mass% or more. The content of the compound (A1) in the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more preferably, from the viewpoint of pattern formability and solvent resistance. Is 7.5% by mass or less, more preferably 3.5% by mass or less, and still more preferably 2.8% by mass or less.

  The content of aniline black (A2) in the resin composition is preferably 1.5% by mass or more, more preferably 5.0% by mass or more, and still more preferably 7, from the viewpoints of pattern formability and solvent resistance. It is 0 mass% or more, More preferably, it is 7.8 mass% or more. The content of aniline black (A2) in the resin composition is preferably 36% by mass or less, more preferably 27% by mass or less, still more preferably 18% by mass or less, and further preferably 10% by mass from the viewpoint of light shielding properties. In the following, it is more preferably 9.0% by mass or less, further preferably 8.0% by mass or less, further preferably 7.5% by mass or less, and further preferably 5.5% by mass or less.

The content of the dispersant (B) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, from the viewpoint of dispersibility. From the viewpoint of light shielding properties and solvent resistance, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
From the viewpoint of dispersibility, the content of the dispersant (B) with respect to 100 parts by mass of the compound (A1) and aniline black (A2) in the resin composition is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. More preferably, it is 10 parts by mass or more, still more preferably 15 parts by mass or more, and from the viewpoint of light shielding properties and solvent resistance, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass. Part or less, more preferably 25 parts by weight or less.

  The content of the organic solvent (C) in the resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more from the viewpoint of workability and dispersibility. From the viewpoint of property, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

The content of the curable compound (D) in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and further preferably from the viewpoint of obtaining solvent resistance and good film hardness. Is 0.6% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less, from the viewpoint of light shielding properties and developability.
The content of the curable compound (D) with respect to 100 parts by mass in total of the compound (A1) and the aniline black (A2) in the resin composition is preferably 3 parts by mass or more from the viewpoint of obtaining solvent resistance and good film hardness. More preferably, it is 5 parts by mass or more, more preferably 6 parts by mass or more, and from the viewpoint of light shielding properties and developability, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 20 parts by mass or less. It is.

The content of the alkali-soluble resin (E) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more, from the viewpoint of pattern formation. From the viewpoint of obtaining good properties and good film strength, it is preferably 10% by mass or less, more preferably 8% by mass or less, and more preferably 6% by mass or less.
The content of the alkali-soluble resin (E) with respect to 100 parts by mass in total of the compound (A1) and the aniline black (A2) in the resin composition is preferably 10 parts by mass or more, more preferably 20 parts by mass from the viewpoint of pattern formation. Part or more, more preferably 30 parts by weight or more, and from the viewpoint of obtaining solvent resistance and good film strength, preferably 100 parts by weight or less, more preferably 80 parts by weight or less, and even more preferably 60 parts by weight or less. .

  When the resin composition of the present invention contains a thiol compound, the content of the thiol compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass, from the viewpoint of solvent resistance. From the viewpoint of dispersion stability, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more. 1% by mass or less.

  When the resin composition of the present invention contains a fluorine compound, the content of the fluorine compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.00%, from the viewpoints of insulation and solvent resistance. 2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.35% by mass or more, and from the viewpoint of the physical properties of the coating film, preferably 2% by mass or less, more preferably 1% by mass or less. More preferably, it is 0.5% by mass or less.

The content of the photopolymerization initiator with respect to 100 parts by mass of the curable compound (D) in the resin composition is preferably 1 part by mass or more, more preferably 50 parts by mass or more, and still more preferably from the viewpoint of obtaining good film hardness. 100 parts by mass or more, still more preferably 120 parts by mass or more, preferably 300 parts by mass or less, more preferably 250 parts by mass or less, and still more preferably 200 parts by mass or less. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.
The content of the photoinitiating auxiliary with respect to 100 parts by mass of the curable compound (D) in the resin composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably from the viewpoint of obtaining good film hardness. It is 5 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.

[Production method]
It is preferable that the manufacturing method of the resin composition of this invention has the following process.
Step 1: Step of obtaining a dispersion containing compound (A1), aniline black (A2), dispersant (B) and organic solvent (C), and optionally an alkali-soluble resin (E) and a thiol compound Step 2 : A step of mixing the dispersion obtained in the above step, the curable compound (D), and, if necessary, an alkali-soluble resin (E), a fluorine compound, a photopolymerization initiator, and a photoinitiator aid.

[Step 1]
Step 1 of the manufacturing method includes the following step 1a or steps 1b-1 to 1b-3.
Step 1a: Step of obtaining a dispersion by dispersing compound (A1), aniline black (A2), dispersant (B) and organic solvent (C), if necessary, alkali-soluble resin (E) and thiol compound 1b-1: A step of dispersing the compound (A1), the dispersant (B) and the organic solvent (C), and, if necessary, the alkali-soluble resin (E) and the thiol compound to obtain a dispersion b1 Step 1b-2: Step of dispersing aniline black (A2), dispersant (B) and organic solvent (C), if necessary, alkali-soluble resin (E) and thiol compound to obtain dispersion b2 Step 1b-3: Dispersion b1 And b2 are mixed to obtain a dispersion. In the resin composition of the present invention, at least two kinds of compounds (A1) and aniline black (A2) are used as the black color material. These compounds (A1) and aniline black (A2) may be dispersed together (the above step 1a) or may be dispersed separately (steps 1b-1 to 1b-3). Among these, it is preferable to disperse the compound (A1) and aniline black (A2) together from the viewpoints of light shielding properties and pattern forming properties (Step 1a).

Various known dispersers can be used as the mixing disperser used in the dispersion in step 1. For example, a high-speed stirring and mixing apparatus such as a homomixer, a kneader such as a roll mill, a kneader, or an extruder, a high-pressure disperser such as a high-pressure homogenizer, a media-type disperser such as a paint shaker or a bead mill can be used. These devices can be used in combination.
Among these, from the viewpoint of uniformly mixing the black color material in the organic solvent, a high-speed stirring and mixing device such as a homomixer, and a media type dispersing machine such as a paint shaker or a bead mill are preferable. Commercially available media type dispersers include “Ultra Apex Mill” manufactured by Kotobuki Industries Co., Ltd., “Picomill” manufactured by Asada Tekko Co., Ltd., and the like.
In the case of using a media type disperser, the material of the media used in the dispersion step is preferably a ceramic material such as zirconia or titania, a polymer material such as polyethylene or nylon, a metal, or the like, and zirconia is preferred from the viewpoint of wear. The diameter of the media is preferably 0.003 mm or more, more preferably 0.01 mm or more, preferably 0.5 mm or less, more preferably 0.4 mm, from the viewpoint of crushing the aggregated particles in the black color material. It is as follows.
The dispersion time is preferably 0.3 hours or more from the viewpoint of sufficiently miniaturizing the black color material, more preferably 1 hour or more, and 50 hours or less from the viewpoint of production efficiency of the dispersion and suppression of reaggregation due to overdispersion. Is preferable, and 10 hours or less is more preferable.

  The dispersion of the present invention contains compound (A1), aniline black (A2), dispersant (B), and organic solvent (C). The dispersion of the present invention is a dispersion of compound (A1) and aniline black (A2), that is, a black color material dispersion.

The total content of compound (A1) and aniline black (A2) in the dispersion is preferably 6% by mass or more, more preferably 10% by mass or more, and still more preferably 16% by mass from the viewpoints of light shielding properties and productivity. From the viewpoint of dispersibility and solvent resistance, it is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.
The content of the compound (A1) in the dispersion is preferably 0.6% by mass or more, more preferably 2.0% by mass or more, still more preferably 4.0% by mass or more, further preferably from the viewpoint of light shielding properties. Is 5.0% by mass or more, more preferably 6.0% by mass or more, and still more preferably 8.0% by mass or more. The content of the compound (A1) in the dispersion is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably, from the viewpoint of pattern formability and solvent resistance. It is 7.0 mass% or less, More preferably, it is 5.5 mass% or less.
The content of aniline black (A2) in the dispersion is preferably 3.0% by mass or more, more preferably 10% by mass or more, and still more preferably 14% by mass or more, from the viewpoint of pattern formability and solvent resistance. More preferably, it is 16 mass% or more. The content of aniline black (A2) in the dispersion is preferably 54% by mass or less, more preferably 36% by mass or less, still more preferably 20% by mass or less, and still more preferably 18% by mass or less, from the viewpoint of light shielding properties. More preferably, it is 16 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 11 mass% or less.

The content of the dispersant (B) in the dispersion is preferably 0.2% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more from the viewpoint of dispersibility. From the viewpoint of solvent resistance, it is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 6% by mass or less.
The preferable range of the content of the dispersant (B) with respect to 100 parts by mass of the compound (A1) and the aniline black (A2) in the dispersion is the same as the preferable range of the content in the resin composition.
From the viewpoint of workability and dispersibility, the content of the organic solvent (C) in the dispersion is preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. And from a viewpoint of the compounding freedom degree of a resin composition, Preferably it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less.
The dispersion of this invention is obtained by the said process 1a or the process 1b-1 to 1b-3, for example.

[Step 2]
In step 2, optional components such as an alkali-soluble resin (E), a thiol compound, a fluorine compound, a photopolymerization initiator, and a photoinitiator aid are mixed as necessary.
Although there is no restriction | limiting in particular in the mixing method of the process 2, For example, stirring with a roller type stirrer is mentioned. The stirring time is preferably 5 minutes or longer, more preferably 15 minutes or longer, from the viewpoint of production efficiency, preferably 10 hours or shorter, more preferably 1 hour or shorter.

[Color filter]
The resin composition of the present invention is preferably used for producing a color filter, more preferably used for forming a black matrix of the color filter.
The method for producing a color filter having a black matrix formed using the resin composition of the present invention is a process of applying a resin composition of the present invention on a substrate, drying, photocuring, and developing to obtain a coating film. (A), a step (b) of forming a black matrix comprising a cured film by heating the coating film obtained in the step (a) to 200 to 300 ° C., and an organic solvent solution of a resin on the cured film It is preferable to have a step (c) of forming a resin film by coating.

After the application of the step (a), it is preferable to dry the organic solvent and to heat or reduce the pressure from the viewpoint of the smoothness and productivity of the coating film.
In the photocuring, for example, the coating film is irradiated with ultraviolet rays, and the polyfunctional monomer in the resin composition undergoes a crosslinking reaction to cure the coating film. Photocuring is performed to leave a pattern on the glass substrate in the subsequent development, and it is preferable not to cure the portion removed by development by placing a photomask for preventing ultraviolet rays.
In the above development, for example, the photocured cured coating film is immersed in an alkaline aqueous solution and further rinsed with water to remove uncured portions.
Step (b) is a post-baking step, and by performing this step, a cured film having excellent hardness can be formed.
The resin in step (c) is, for example, polyimide. The organic solvent in the step (c) is NMP, for example.

  In relation to the above-described embodiment, the present invention further discloses the following resin composition, color filter, dispersion, production method thereof and the like.

〔上記式（１）中、Ｘは二重結合を示し、幾何異性体としてそれぞれ独立にＥ体又はＺ体であり、Ｒ^１は、各々独立に、水素原子、メチル基、ニトロ基、メトキシ基、臭素原子、塩素原子、フッ素原子、カルボキシ基、又はスルホン酸基を示し、Ｒ^２は、各々独立に、水素原子、メチル基、又はフェニル基を示し、Ｒ^３は、各々独立に、水素原子、メチル基、又は塩素原子を示す。〕[1] A compound (A1) represented by the following formula (1), aniline black (A2), a dispersant (B), an organic solvent (C), and a curable compound (D) are contained. A colored curable resin composition having a mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) of 0.10 or more and 0.50 or less.

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom. Represents a methyl group or a chlorine atom. ]

[2] The colored curable resin composition according to [1], wherein R ¹ is preferably bonded to the 6-position of the dihydroindolone ring.
[3] The colored curable resin composition according to [1] or [2], wherein R ³ is preferably bonded to the 4-position of the dihydroindolone ring.
[4] The colored curable resin composition according to any one of [1] to [3], wherein R ¹ , R ² , and R ³ are preferably hydrogen atoms.
[5] The average particle size of aniline black (A2) is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.24 μm or more, still more preferably 0.27 μm or more, and further preferably 0.8. 30 μm or more, more preferably 0.35 μm or more, preferably 1.5 μm or less, more preferably 1.0 μm or less, still more preferably 0.7 μm or less, and even more preferably 0.5 μm or less, [1] to [4] The colored curable resin composition according to any one of [4].
[6] The BET specific surface area of aniline black (A2) is preferably 34 m ² / g or less, more preferably 17 m ² / g or less, still more preferably 14 m ² / g or less, still more preferably 12 m ² / g or less, and further Preferably it is 11 m < ² > / g or less, Preferably it is 2.2 m < ² > / g or more, More preferably, it is 3.3 m < ² > / g or more, More preferably, it is 4.7 m < ² > / g or more, More preferably, it is 6.6 m < ² > / g. The colored curable resin composition according to any one of [1] to [5], which is g or more.
[7] The mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) is preferably 0.15 or more, more preferably 0.20 or more, still more preferably Is not less than 0.24, more preferably not less than 0.28, preferably not more than 0.40, more preferably not more than 0.35, still more preferably not more than 0.32, any one of [1] to [6] A colored curable resin composition according to claim 1.
[8] The mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) is preferably 0.28 or less, more preferably 0.26 or less, still more preferably Is a colored curable resin composition according to any one of [1] to [7], which is 0.25 or less.

[9] The dispersant (B) is a polyurethane-based dispersant, a polyamide-based dispersant, a polyimide-based dispersant, a polycarboxylic acid-based dispersant, a polyamine-based dispersant, and a quaternary ammonium salt or the like is introduced into a part thereof. The colored curable resin composition according to any one of [1] to [8], which is at least one selected from among dispersants.
[10] The dispersant (B) is preferably a reaction between a polyamine compound having 1 to 5 nitrogen atoms and a quaternizing agent having an average addition mole number of 1 to 100 and having a lactone chain or an alkyleneoxy chain. The colored curable resin composition according to any one of [1] to [9], which is a dispersant (B1) obtained in this manner.
[11] The equivalent ratio of the quaternizing agent to the equivalent of the polyamine compound [quaternizing agent equivalent / polyamine equivalent] is preferably 0.3 or more, more preferably 0.6 or more, and 1.0 or less. The colored curable resin composition according to any one of [1] to [10], which is preferably 0.9 or less.
[12] The organic solvent (C) is preferably at least one selected from the group consisting of ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate and propylene glycol monoethyl ether acetate. The colored curable resin composition according to any one of [1] to [11], which is a seed, more preferably propylene glycol monomethyl ether acetate.
[13] The colored curable resin composition according to [1] to [12], wherein the curable compound (D) is preferably a polyfunctional polymerizable compound.
[14] The colored curable resin composition according to [13], wherein the polyfunctional polymerizable compound is preferably a polyfunctional (meth) acrylate compound.
[15] The number of ethylenically unsaturated bonds contained in the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, preferably 8 or less, more The colored curable resin composition according to [13] or [14], which is preferably 7 or less, more preferably 6 or less.
[16] The polyfunctional polymerizable compound is preferably trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipenta The colored curable resin composition according to any one of [13] to [15], which is at least one selected from erythritol hexa (meth) acrylate, more preferably dipentaerythritol hexaacrylate.

[17] The colored curable resin composition according to any one of [1] to [16], preferably further containing an alkali-soluble resin (E).
[18] The colored curable resin composition according to [17], wherein the alkali-soluble resin (E) is preferably a copolymer of (meth) acrylic acid ester and (meth) acrylic acid.

[19] The colored curable resin composition according to any one of [1] to [18], which further preferably contains a thiol compound, more preferably a polyvalent thiol compound.
[20] The number of mercapto groups possessed by the thiol compound is preferably 3 or more, more preferably 4 or more, preferably 9 or less, more preferably 8 or less, still more preferably 7 or less, and even more. The colored curable resin composition according to [19], preferably 6 or less.
[21] The thiol compound is preferably an aliphatic thiol compound, a thiol compound having a cyclic structure such as a heterocyclic ring or an aromatic ring, and more preferably an aliphatic thiol compound, according to [19] or [20] Colored curable resin composition.
[22] The thiol compound is preferably pentaerythritol tetrakis (3-mercaptopropionate), tris (3-mercaptopropionic acid) trimethylolpropane, 1,3,5-tris (3-mercaptobutyryloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, dipentaerythritol hexakis (3-mercaptopropionate) and tris-[(3-mercaptopropionyloxy) -ethyl] -At least one selected from isocyanurates, more preferably at least one selected from pentaerythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate), More preferably pentaerythritol A Rakisu (3-mercaptopropionate), colored curable resin composition according to any one of [19] - [21].

[23] The colored curable resin composition according to any one of [1] to [22], which preferably contains a fluorine compound.
[24] The fluorine compound is preferably at least one selected from a surfactant having a fluorocarbon chain, a fluorine-based oligomer, a compound having a fluorocarbon chain and an ethylenically unsaturated bond, and the like. Colored curable resin composition.
[25] The fluorine compound is preferably a fluorine-based oligomer and at least one compound selected from a compound having a fluorocarbon chain and an ethylenically unsaturated bond, more preferably a compound having a fluorocarbon chain and an ethylenically unsaturated bond. [23] or the colored curable resin composition according to [24].

[26] The colored curable resin composition according to any one of [1] to [25], which preferably further contains a photopolymerization initiator.
[27] The colored curable resin composition according to [26], preferably further containing a photoinitiator auxiliary.

[28] The total content of the compound (A1) and aniline black (A2) in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. Is at most 40 mass%, more preferably at most 30 mass%, even more preferably at most 25 mass%, even more preferably at most 20 mass%, even more preferably at most 15 mass%, any one of [1] to [27] The colored curable resin composition described in 1.
[29] The content of the compound (A1) in the resin composition is preferably 0.3% by mass or more, more preferably 1.0% by mass or more, still more preferably 2.0% by mass or more, and further preferably 2%. The colored curable resin composition according to any one of [1] to [28], which is 0.5% by mass or more, more preferably 3.0% by mass or more, and further preferably 4.0% by mass or more.
[30] The content of the compound (A1) in the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 7.5% by mass or less, More preferably, it is 3.5 mass% or less, More preferably, it is 2.8 mass% or less, The colored curable resin composition in any one of [1]-[29].
[31] The content of aniline black (A2) in the resin composition is preferably 1.5% by mass or more, more preferably 5.0% by mass or more, still more preferably 7.0% by mass or more, and still more preferably. The colored curable resin composition according to any one of [1] to [30], which is 7.8% by mass or more.
[32] The content of aniline black (A2) in the resin composition is preferably 36% by mass or less, more preferably 27% by mass or less, still more preferably 18% by mass or less, still more preferably 10% by mass or less, and further Preferably it is 9.0 mass% or less, More preferably, it is 8.0 mass% or less, More preferably, it is 7.5 mass% or less, More preferably, it is 5.5 mass% or less, Any of [1]-[31] A colored curable resin composition according to claim 1.

[33] The content of the dispersant (B) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 10%. The colored curable resin composition according to any one of [1] to [32], which is not more than mass%, more preferably not more than 5 mass%, still more preferably not more than 3 mass%.
[34] The content of the dispersant (B) with respect to 100 parts by mass in total of the compound (A1) and the aniline black (A2) in the resin composition is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably. Is 10 parts by mass or more, more preferably 15 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less. The colored curable resin composition according to any one of [1] to [33].
[35] The content of the organic solvent (C) in the resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 95% by mass or less. More preferably, it is 90 mass% or less, More preferably, it is 85 mass% or less, The colored curable resin composition in any one of [1]-[34].

[36] The content of the curable compound (D) in the resin composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.6% by mass or more. The colored curable resin composition according to any one of [1] to [35], which is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.
[37] The content of the curable compound (D) with respect to a total of 100 parts by mass of the compound (A1) and the aniline black (A2) in the resin composition is preferably 3 parts by mass or more, more preferably 5 parts by mass or more. The colored curable resin according to any one of [1] to [36], which is preferably 6 parts by mass or more, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 20 parts by mass or less. Composition.

[38] The content of the alkali-soluble resin (E) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass with respect to the solid content in the resin composition. % Or more, preferably 10% by mass or less, more preferably 8% by mass or less, more preferably 6% by mass or less, the colored curable resin composition according to [17] or [18].
[39] The content of the alkali-soluble resin (E) with respect to 100 parts by mass in total of the compound (A1) and the aniline black (A2) in the resin composition is preferably 10 parts by mass or more, more preferably 20 parts by mass or more. Preferably it is 30 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 60 parts by mass or less, according to any of [17], [18] and [38] Colored curable resin composition.
[40] The content of the thiol compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and still more preferably 0.00%. The colored curable resin composition according to any one of [19] to [22], which is 4% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less. object.
[41] The content of the fluorine compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and even more preferably 0.00%. 35% by mass or more, preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and the color curable properties according to any one of [23] to [25] Resin composition.
[42] The content of the photopolymerization initiator with respect to 100 parts by mass of the curable compound (D) in the resin composition is preferably 1 part by mass or more, more preferably 50 parts by mass or more, and further preferably 100 parts by mass or more. The colored curable resin composition according to [26] or [27], which is preferably 120 parts by mass or more, preferably 300 parts by mass or less, more preferably 250 parts by mass or less, and still more preferably 200 parts by mass or less. object.
[43] The content of the photoinitiator auxiliary with respect to 100 parts by mass of the curable compound (D) in the resin composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more. The colored curable resin composition according to [27], which is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.

[44] A method for producing a colored curable resin composition, comprising the following steps.
Step 1: Step of obtaining a dispersion containing compound (A1), aniline black (A2), dispersant (B) and organic solvent (C) Step 2: Dispersion obtained in the above step and curable compound ( D) and a step of mixing the alkali-soluble resin (E) and the fluorine compound as necessary

[45] The process for producing a colored curable resin composition according to [44], further comprising an alkali-soluble resin (E) in Step 1.
[46] The method for producing a colored curable resin composition according to [44] or [45], further including a thiol compound in the step 1.
[47] The method for producing a colored curable resin composition according to any one of [44] to [46], wherein in step 2, an alkali-soluble resin (E) is preferably further mixed.
[48] The process for producing a colored curable resin composition according to any one of [44] to [47], wherein in step 2, a fluorine compound is preferably further mixed.
[49] The process for producing a colored curable resin composition according to any one of [44] to [48], wherein in step 2, a photopolymerization initiator is further mixed.
[50] The method for producing a colored curable resin composition according to any one of [44] to [49], wherein in step 2, a photoinitiator is further mixed.
[51] The method for producing a colored curable resin composition according to any one of [44] to [50], wherein the step 1 preferably includes the following step 1a or steps 1b-1 to 1b-3.
Step 1a: Step of obtaining a dispersion by dispersing compound (A1), aniline black (A2), dispersant (B) and organic solvent (C), if necessary, alkali-soluble resin (E) and thiol compound 1b-1: A step of dispersing the compound (A1), the dispersant (B) and the organic solvent (C), and, if necessary, the alkali-soluble resin (E) and the thiol compound to obtain a dispersion b1 Step 1b-2: Step of dispersing aniline black (A2), dispersant (B) and organic solvent (C), if necessary, alkali-soluble resin (E) and thiol compound to obtain dispersion b2 Step 1b-3: Dispersion b1 And a step of mixing b2 to obtain a dispersion [52] The process for producing a colored curable resin composition according to [51], wherein the step 1 is preferably the step 1a.

〔上記式（１）中、Ｘは二重結合を示し、幾何異性体としてそれぞれ独立にＥ体又はＺ体であり、Ｒ^１は、各々独立に、水素原子、メチル基、ニトロ基、メトキシ基、臭素原子、塩素原子、フッ素原子、カルボキシ基、又はスルホン酸基を示し、Ｒ^２は、各々独立に、水素原子、メチル基、又はフェニル基を示し、Ｒ^３は、各々独立に、水素原子、メチル基、又は塩素原子を示す。〕[53] A compound (A1) represented by the following formula (1), aniline black (A2), a dispersant (B), and an organic solvent (C) are contained, and the compound (A1) and aniline black ( Dispersion whose mass ratio [A1 / (A1 + A2)] of compound (A1) with respect to the sum total with A2) is 0.10 or more and 0.50 or less.

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom. Represents a methyl group or a chlorine atom. ]

[54] The total content of the compound (A1) and aniline black (A2) in the dispersion is preferably 8% by mass or more, more preferably 10% by mass or more, and further preferably 16% by mass or more, preferably The dispersion according to [53], which is 60% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.
[55] The content of the compound (A1) in the dispersion is preferably 0.6% by mass or more, more preferably 2.0% by mass or more, still more preferably 4.0% by mass or more, and still more preferably 5. The dispersion according to [53] or [54], which is 0% by mass or more, more preferably 6.0% by mass or more, and further preferably 8.0% by mass or more.
[56] The content of the compound (A1) in the dispersion is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 7.0% by mass or less, and further The dispersion according to any one of [53] to [55], which is preferably 5.5% by mass or less.
[57] The content of aniline black (A2) in the dispersion is preferably 3.0% by mass or more, more preferably 10% by mass or more, still more preferably 14% by mass or more, and further preferably 16% by mass or more. The dispersion according to any one of [53] to [56].
[58] The content of aniline black (A2) in the dispersion is preferably 54% by mass or less, more preferably 36% by mass or less, still more preferably 20% by mass or less, still more preferably 18% by mass or less, and still more preferably. The dispersion according to any one of [53] to [57], which is 16% by mass or less, more preferably 15% by mass or less, and still more preferably 11% by mass or less.
[59] The content of the dispersant (B) in the dispersion is preferably 0.2% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and preferably 20% by mass or less. The dispersion according to any one of [53] to [58], more preferably 10% by mass or less, and still more preferably 6% by mass or less.
[60] The content of the dispersant (B) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass with respect to 100 parts by mass in total of the compound (A1) and aniline black (A2). Above, still more preferably 15 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less, [53] to [59] The dispersion according to any one of [59].
[61] The content of the organic solvent (C) in the dispersion is preferably 40% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 95% by mass or less. The dispersion according to any one of [53] to [60], which is preferably 90% by mass or less, more preferably 80% by mass or less.
[62] The dispersion according to any of [53] to [61], preferably having the limitations described in [2] to [18].

[63] Use of the colored curable resin composition according to any one of [1] to [43] for producing a color filter.
[64] Use of the colored curable resin composition according to any one of [1] to [43] for forming a black matrix of a color filter.

[65] A color filter comprising a black matrix formed using the colored curable resin composition according to any one of [1] to [43].
[66] A step (a) in which the colored curable resin composition according to any one of [1] to [43] is applied on a substrate, dried, photocured, and developed to obtain a coating film; A step (b) of forming the black matrix made of a cured film by heating the coating film obtained in a) to 200 to 300 ° C., and forming a resin film by applying an organic solvent solution of resin on the cured film The manufacturing method of a color filter which has the process (c) to do.

  Evaluation of light-shielding property and pattern forming property, weight average molecular weight, solid content, and measurement of BET specific surface area and average particle size of aniline black were performed by the following methods.

(1) Evaluation of light shielding property The resin composition was applied on a 10 cm × 10 cm glass substrate with a spin coater (“ACT-220DII” manufactured by Active Corporation). The substrate was allowed to stand for 5 minutes on a horizontal platform, left for 10 minutes on a 120 ° C. hot plate, and further treated in a clean oven at 230 ° C. for 20 minutes to obtain a substrate having a coating film on one side. The thickness of the coating film was adjusted to 1 to 2 μm. Tabletop transmission densitometer (X-Rite Corp. "Model 361T", measurement wavelength 550 nm) using a measuring absorbance of the substrate, the measured value was OD _R. The thickness T (μm) of the coating film at the site where the absorbance was measured was measured with “SURFCOM 1500DX” manufactured by Tokyo Seimitsu Co., Ltd. The optical density per 1 μm thickness of the coating film was defined as “OD” and calculated by the following formula.
OD = OD _R / T (μm)
The greater the OD, the better the light shielding property.

(2) Evaluation of pattern formability A resin composition was applied onto a 10 cm × 10 cm glass substrate using a spin coater (“ACT-220DII” manufactured by Active Corporation), and the substrate was subjected to 2 on a hot plate at 100 ° C. The substrate was left for 1 minute to obtain a substrate having a coating film on one side. The thickness of the coating film was set to 1 μm. A photomask was placed on the surface of the substrate on which the resin composition was applied, with a distance of 0.5 mm from the substrate. The photomask has slits with widths (unit: μm) 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100. Using a UV fiber spot irradiation device “MUV-202U” manufactured by Moritex Co., Ltd., the substrate was irradiated with 100 mJ / cm ^{2 of} ultraviolet rays through the photomask. The photomask was removed, the substrate was immersed in a 0.04 mass% KOH aqueous solution for 2 minutes, rinsed with pure water, and heat-treated in a 230 ° C. clean oven for 20 minutes. Using an optical microscope, thin lines on the substrate developed with the photomask were observed, and the thinnest line width remaining on the substrate was defined as the remaining thin line width. The smaller the remaining fine line width, the better the pattern forming property.

(3) Measurement of weight average molecular weight <Condition 1>
Gel permeation chromatography (hereinafter also referred to as “GPC”) was used. As an eluent, an N, N-dimethylformamide (hereinafter also referred to as “DMF”) solution having a phosphoric acid concentration of 60 mmol / L and a lithium bromide concentration of 50 mmol / L was used. The sample was diluted with DMF to obtain a solution having a solid content of 0.3% by mass, and 0.1 mL of the solution was diluted with GPC [apparatus: “HLC-8120GPC” manufactured by Tosoh Corporation, column: “TSK-GEL, manufactured by Tosoh Corporation” α-M ”× 2 and flow rate: 1 mL / min].
<Condition 2>
A gel chromatography method (GPC method, apparatus: “HLC-8320GPC” manufactured by Tosoh Corporation) was prepared by using, as an eluent, a solution obtained by dissolving dimethyldodecylamine (“Farmin DM20” manufactured by Kao Corporation) at 1 mmol / L in chloroform. ”, Detector: differential refractometer attached to the apparatus, column:“ K-804L ”× 2, manufactured by Showa Denko KK, flow rate: 1.0 mL / min, column temperature: 40 ° C.). The following monodisperse polystyrene was used as a standard substance.
In both condition 1 and condition 2, as standard materials, Tosoh Corporation standard polystyrene “A-500 (Mw = 5.0 × 10 ² )”, “A-2500 (Mw = 2.63 × 10 ³ )”, “F-1 (Mw = 1.02 × 10 ⁴ )” and “F-10 (Mw = 9.64 × 10 ⁴ )” were used.

(4) Measurement of solid content A glass rod and 10 g of dry anhydrous sodium sulfate were placed in a petri dish, and 2 g of a sample was weighed and mixed with the glass rod, and dried for 2 hours with a vacuum dryer (pressure 8 kPa) at 105 ° C. The mass after drying was measured, and the value obtained from the following formula was used as the solid content of the sample.
Solid content (mass%) = [[mass after drying− (petri dish + glass rod + mass of anhydrous sodium sulfate)] / mass of sample] × 100

(5) Measurement of BET specific surface area and average particle diameter of aniline black Using a specific surface area measuring device (“Flowsorb III 2310” manufactured by Shimadzu Corporation), using nitrogen as a measurement gas, BET specific surface area S _m (unit: m ² / g) was measured.
Using the value of the obtained BET specific surface area, R (unit: nm) obtained from the following formula was defined as the average particle diameter.
R = 6000 / (d × S _m )
d: True density (g / cm ³ ) S _m : Specific surface area (m ² / g)

Synthesis Example 1 [Synthesis of Compound A1-1]
115 g of 2,5-dihydroxybenzene-1,4-diacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a 5 L four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube, Dean-Stark tube and Dimroth tube. , 150 g of isatin (manufactured by Tokyo Chemical Industry Co., Ltd.), 35 g of p-toluenesulfonic acid monohydrate and 3750 g of toluene were heated to 110 ° C., stirred for 7 hours while dehydrating, and further stirred at 110 ° C. for 14 hours. did. The mixture was cooled to room temperature, and the black suspension was filtered with filter paper No. 2 (Advantech Toyo Co., Ltd.). This filtration residue was washed with 5 L of methanol and dried at 60 ° C./104 Pa to obtain 236 g of compound A1-1 (black substance) of the following formula (A1-1).

This black substance was dissolved in DMF, and ESI / MS measurement by liquid chromatography mass spectrometry was performed to confirm that the molecular weight was 448.07.

Synthesis Example 2 [Synthesis of alkali-soluble resin (copolymer of benzyl methacrylate and methacrylic acid)]
In a separable flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 3.6 g of methacrylic acid (hereinafter also referred to as “MAA”), 36.4 g of benzyl methacrylate (hereinafter also referred to as “BzMA”), 3-mercaptopropionic acid 0.56g and PGMEA 40g were prepared, and nitrogen substitution was performed, stirring.
While stirring the flask, the temperature was raised to 78 ° C., MAA 14.4 g, BzMA 145.6 g, 3-mercaptopropionic acid 2.2 g, PGMEA 160 g, and 2,2′-azobis (2,4-dimethylvaleronitrile). ) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter also referred to as “V-65”)) A solution obtained by mixing 2.0 g was added dropwise over 3 hours. After completion of dropping, a mixed solution of 2.0 g of V-65 and 10.0 g of PGMEA was added and stirred at 78 ° C. for 1 hour. Furthermore, a mixed solution of 1.0 g of V-65 and 10.0 g of PGMEA was added and stirred at 78 ° C. for 1 hour. PGMEA 100g was added, it cooled, stirring, and the PGMEA solution of the copolymer (henceforth "the copolymer 1") of BzMA and MAA was obtained. The solid content was 40% by mass, and the weight average molecular weight of Copolymer 1 was 10900 (measured value under <Condition 1>).

(Preparation of clear resist solution)
42.2 g of the copolymer 1 solution having a solid content of 40.0% by mass obtained in Synthesis Example 2, DPHA 6.64 g, photopolymerization initiator (“IRGACURE OXE02” manufactured by BASF Japan Ltd.) 11.07 g, PGMEA 80 g and 60 g of cyclohexanone were uniformly mixed to obtain a clear resist solution.

Synthesis Example 3-a1 [Polyester a1: Synthesis of lauryloxypoly (ε-caprolactone) (21)]
In a 10 L flask equipped with a stirrer, a thermometer, and a nitrogen blowing tube, 350 g (1.89 mol) of lauryl alcohol (“Kalcoal 2098” manufactured by Kao Corporation), ε-caprolactone (manufactured by Tokyo Chemical Industry Co., Ltd.) 4, 500 g (39.4 mol) and 0.0606 g of tetrabutyl orthotitanate were charged, and stirring was started. The flask was purged with nitrogen, reacted at 150 ° C. for 2 hours, and further reacted at 170 ° C. for 5 hours. Then, it cooled to room temperature and obtained lauryl oxypoly ((epsilon) -caprolactone) (21) (polyester a1).

Synthesis Example 3-b1 [chloroacetate b1: synthesis of lauryloxypoly (ε-caprolactone) (21) monochloroacetate]
In a 10 L flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube, 4,790 g of polyester a1 obtained in Synthesis Example 3-a1, monochloroacetic acid (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) 199 g, 17.5 g of p-toluenesulfonic acid monohydrate (manufactured by Kishida Chemical Co., Ltd., special grade reagent) was charged and stirring was started. The flask was purged with nitrogen, reacted at 140 ° C. and atmospheric pressure for 2 hours, and further reacted under reduced pressure conditions of 140 ° C. and −0.1 MPaG (gauge pressure) for 21 hours while blowing nitrogen. Then, it returned to atmospheric pressure with nitrogen, cooled to 80 degreeC, hydrosartite (Kyowa Chemical Industry Co., Ltd. "KYOWARD 500SH") 131.8g was added, and it stirred at 80 degreeC for 3 hours. The obtained liquid was kept at 80 ° C. and filtered with a filter paper (“No. 5A” manufactured by Advantech Toyo Co., Ltd.) to obtain lauryloxypoly (ε-caprolactone) (21) monochloroacetate (chloroacetate b1).

Synthesis Example 3 [Dispersant B-2: N, N, N ′, N′-tetramethyl-N, N′-bis [lauryloxypoly (ε-caprolactone) (21) carbonylmethylene] -propanediammonium chloride Composition]
In a 500 mL separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer, 200 g of chloroacetate b1 obtained in Synthesis Example 3-b1, N, N, N ′, N′-tetramethylpropanediamine (Kao Riser No. 2 manufactured by Kao Corporation) 5.04 g was charged and stirring was started. The flask was purged with nitrogen and reacted at 80 ° C. for 20 hours. Addition of 300 g of propylene glycol monomethyl ether acetate (PGMEA), stirring at 80 ° C. for 1 hour, cooling to room temperature, and dispersing agent B-2: N, N, N ′, N′-tetramethyl-N, N ′ A PGMEA solution of bis [lauryloxypoly (ε-caprolactone) (21) carbonylmethylene] -propanediammonium chloride was obtained. The solid content of the solution was 39.8% by mass, and the weight average molecular weight was 9,800 (measured value according to <Condition 2>).

Example 1 (Production of Dispersion 1)
15.0 g of compound A1-1 obtained in Synthesis Example 1, aniline black A2-1 (“Toshiki 5030 conc” manufactured by Tokyo Color Material Industries Co., Ltd., BET specific surface area: 10.9 m ² / g, true density: 1.42 g / Cm ³ , average particle size: 388 nm) 15.0 g, “Soluth J-200” 5.3 g manufactured by Nippon Lubrizol Co., Ltd. as a dispersant, 109.1 g PGMEA as an organic solvent, and zirconia beads having a diameter of 0.3 mm 300 g ("YTZ ball" manufactured by Nikkato) was put in a 500 mL polyethylene container and stirred for 3 hours at 640 rpm with "Paint Shaker" manufactured by Asada Tekko Co., Ltd. From the obtained dispersion, zirconia beads were removed by filtration, and 5.6 g of the PGMEA solution of copolymer 1 obtained in Synthesis Example 2 was added and mixed to obtain dispersion 1.
(Preparation of resin composition 1)
11.2 g of the dispersion 1 and 10.1 g of the clear resist solution were put into a glass container having a capacity of 30 mL and sealed. Using a roller stirrer (“Mix Rotor Variable VMR-5R” manufactured by AS ONE Co., Ltd.), mixing was performed at 50 rpm for 20 minutes to obtain a resin composition 1.

Examples 2-12, 51-52
(Production of dispersions 2 to 12, 51 to 52)
Dispersions 2 to 12, 51 to 52 were obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was used. In addition, the raw material used for manufacture is as follows.
(Preparation of resin compositions 2-12, 51-52)
Resin compositions 2 to 12, 51 to 52 were obtained in the same manner as in Example 1 except that the formulation shown in Table 2 was used.

A1-1: Compound A1-1 (Synthesis Example 1)
A2-1: Aniline black (“Toshiki 5030 conc” manufactured by Tokyo Color Materials Co., Ltd., BET specific surface area: 10.9 m ² / g, true density: 1.42 g / cm ³ , average particle diameter: 388 nm)
A2-2: Aniline black (A2-1 fine particle type, BET specific surface area: 13.6 m ² / g, true density: 1.47 g / cm ³ , average particle size: 300 nm)
A2-3: Aniline black (A2-1 fine particle type, BET specific surface area: 15.7 m ² / g, true density: 1.51 g / cm ³ , average particle size: 253 nm)
B-1: “Solsperse J200” manufactured by Nippon Lubrizol Corporation
B-2: Dispersant B-2 (Synthesis Example 3)
C-1: PGMEA

  Various evaluation was performed using the obtained resin composition. The results are shown in Table 3.

  According to Examples 1-12, it turns out that the colored curable resin composition excellent in light-shielding property and pattern formation property is obtained with the resin composition of this invention.

  According to the resin composition of the present invention, since it is excellent in light shielding properties and pattern forming properties, it is possible to provide a color filter including a black matrix having excellent performance.

Claims (13)

It contains a compound (A1) represented by the following formula (1), aniline black (A2), a dispersant (B), an organic solvent (C), and a curable compound (D), and a compound (A1 ) And aniline black (A2), the colored curable resin composition having a mass ratio [A1 / (A1 + A2)] of the compound (A1) of from 0.10 to 0.50.

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom. Represents a methyl group or a chlorine atom. ]   The color curable property according to claim 1, wherein the mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of the compound (A1) and aniline black (A2) is 0.20 or more and 0.40 or less. Resin composition.   The colored curable resin composition of Claim 1 or 2 whose sum total content of a compound (A1) and aniline black (A2) is 3 to 40 mass% in a resin composition.   The coloring curable resin composition in any one of Claims 1-3 whose content of a dispersing agent (B) is 0.1 to 10 mass% in a resin composition.   The colored curable resin composition according to any one of claims 1 to 4, wherein the content of the organic solvent (C) is 60% by mass or more and 95% by mass or less in the resin composition.   The colored curable resin composition according to any one of claims 1 to 5, wherein the content of the curable compound (D) is 0.3% by mass or more and 10% by mass or less in the resin composition.   The total content of the compound (A1) and aniline black (A2) is 3% by mass or more and 40% by mass or less in the resin composition, and the content of the dispersant (B) is 0.1% by mass in the resin composition. The content of the organic solvent (C) is 60% by mass or more and 95% by mass or less in the resin composition, and the content of the curable compound (D) is 0.00% in the resin composition. The colored curable resin composition according to any one of claims 1 to 6, which is 3% by mass or more and 10% by mass or less.   The colored curable resin composition according to any one of claims 1 to 7, further comprising an alkali-soluble resin (E).   The colored curable resin composition according to any one of claims 1 to 8, wherein the average particle diameter of aniline black (A2) is 0.24 µm or more and 0.7 µm or less.   The colored curable resin composition according to any one of claims 1 to 9, which is used for forming a black matrix of a color filter.   Use of the colored curable resin composition according to any one of claims 1 to 9 for forming a black matrix of a color filter.   A color filter comprising a black matrix formed using the colored curable resin composition according to claim 1. A compound (A1) represented by the following formula (1), aniline black (A2), a dispersant (B), and an organic solvent (C) are contained, and the compound (A1), aniline black (A2), Dispersion in which the mass ratio [A1 / (A1 + A2)] of the compound (A1) to the total of 0.10 is 0.10 or more and 0.50 or less.

[In the above formula (1), X represents a double bond, and each independently represents an E-form or a Z-form as a geometric isomer, and each R ¹ independently represents a hydrogen atom, a methyl group, a nitro group, or a methoxy group. , A bromine atom, a chlorine atom, a fluorine atom, a carboxy group, or a sulfonic acid group, each R ² independently represents a hydrogen atom, a methyl group, or a phenyl group, and each R ³ independently represents a hydrogen atom. Represents a methyl group or a chlorine atom. ]