JP2017016100A - Coloring curable resin composition, color filter and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring curable resin composition good in storage stability.SOLUTION: There is provided a coloring curable resin composition containing (A) a coloring agent, (B) a resin, (C) a polymerizable compound, (D) a polymerization initiator and (E) a solvent, where the coloring agent (A) contains a compound consisting of anion of a compound containing at least one element selected from a group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen and cation having a dye skeleton and a dye, the solvent (E) contains n kinds of solvents k and an S vale calculated by the following formula is over 8.75 and less than 11.11. (1), where arepresents percentage content of the solvent k to the all solvent, brepresents an SP value of the solvent k based on a Fedors method and n represents an integer of 1 or more.SELECTED DRAWING: None

Description

  The present invention relates to a colored curable resin composition, a color filter, and a display device.

  Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored curable resin composition, a colored curable resin composition containing 4-hydroxy-4-methyl-2-pentanone and propylene glycol monomethyl ether acetate (mass ratio 8: 2) as a solvent (patent) A colored curable resin composition (Patent Document 2) containing only Document 1) and propylene glycol monomethyl ether acetate is known.

JP2015-281121A JP 2014-153570 A

However, when the colored curable resin composition is stored at room temperature, the viscosity of the composition may increase, and the storage stability is not sufficient.
An object of the present invention is to provide a colored curable resin composition having good storage stability.

[1] Contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), and the colorant (A) contains tungsten, molybdenum, silicon and phosphorus. A compound and a dye comprising an anion of a compound containing at least one element selected from the group consisting of oxygen and oxygen, and a cation having a pigment skeleton, and the solvent (E) contains n types of solvents k, and S value is 8.75 (cal / cm ^{3) 1/2} ultra 11.11 (cal / cm ³⁾ colored curable resin composition and less than ^1/2 obtained from equation (1).

［式（１）中、ａ_kは、全溶剤に対する溶剤ｋの含有率を表す。
ｂ_kは、Ｆｅｄｏｒｓ法に基づく溶剤ｋのＳＰ値を表す。
ｎは、１以上の整数を表す。］
［２］ 溶剤（Ｅ）が、ＳＰ値９．０（ｃａｌ／ｃｍ³）^1/2未満の第一溶剤から選択される１種以上と、ＳＰ値９．０（ｃａｌ／ｃｍ³）^1/2以上の第二溶剤から選択される１種以上を含む［１］に記載の着色硬化性樹脂組成物。
［３］ 溶剤（Ｅ）が、沸点１５０℃未満の第三溶剤から選択される１種以上と、沸点１５０℃以上の第四溶剤から選択される１種以上を含む［１］又は［２］に記載の着色硬化性樹脂組成物。
［４］ ［１］〜［３］のいずれかに記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［５］ ［４］に記載のカラーフィルタを含む表示装置。

[In formula (1), _ak represents the content rate of the solvent k with respect to all the solvents.
b _k represents the SP value of the solvent k based on the Fedors method.
n represents an integer of 1 or more. ]
[2] The solvent (E) is at least one selected from first solvents having an SP value of less than 9.0 (cal / cm ³ ) ^1/2, and an SP value of 9.0 (cal / cm ³ ) ^{1 /} The colored curable resin composition according to [1], including one or more selected from ^two or more second solvents.
[3] The solvent (E) includes at least one selected from a third solvent having a boiling point of less than 150 ° C. and at least one selected from a fourth solvent having a boiling point of not less than 150 ° C. [1] or [2] The colored curable resin composition described in 1.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

  According to the present invention, a colored curable resin composition having good storage stability can be provided.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), and the solvent (E) It includes n kinds of solvents k, and S values obtained from a predetermined equation 8.75 (cal / cm ^{3) 1/2} ultra 11.11 (cal / cm ³⁾ is less than ^1/2.
Hereinafter, each component will be described in the order of the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E).

<Colorant (A)>
The colorant (A) is a compound (Aa) comprising a cation having a dye skeleton and an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus (hereinafter referred to as “a”). Compound (Aa)) and dye (Ab). One or more of each of the compound (Aa) and the dye (Ab) may be used.

  The dye skeleton in the present invention refers to a partial structure of a compound having a unique color by selectively absorbing visible light (wavelength: 400 to 750 nm), and the partial structure has a unique color. The structure for expressing is included.

  As the dye skeleton possessed by the cation constituting the compound (Aa), a dye skeleton having an onium structure among azo skeleton, xanthene skeleton, azine skeleton, cyanine skeleton, acridine skeleton, anthraquinone skeleton, squarylium skeleton, etc .; triarylmethane skeleton; And a dye skeleton in which one or more aromatic hydrocarbon rings of the triarylmethane skeleton are aromatic heterocycles. Among them, a dye skeleton in which one or more aromatic hydrocarbon rings of a xanthene skeleton, a triarylmethane skeleton, or a triarylmethane skeleton is an aromatic heterocyclic ring is preferable, and an aromatic hydrocarbon of a triarylmethane skeleton is more preferable. A dye skeleton in which one or more of the rings are aromatic heterocycles.

  As the anion derived from the compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen, for example, a heteropolyacid anion containing tungsten and an isopolyacid anion containing tungsten are preferable. More preferred are phosphotungstate anions, silicotungstate anions and tungsten isopolyacid anions.

Examples of the heteropolyacid anion and isopolyacid anion containing tungsten include Keggin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ and Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^{6. -} , Β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O _{40 ^{] 4-, [P 2 W 17}} O 61] 10-, [P 2 W 15 O 56] 12-, [H 2 P 2 W 12 O 48] 12-, [NaP 5 W 30 O 110] 14-, α- [SiW ₉ O ₃₄ ] ¹⁰⁻ , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures thereof.

  The compound (Aa) is preferably a compound represented by the formula (AI) (hereinafter also referred to as (AI)).

［式（Ａ−Ｉ）中、Ｒ⁴¹〜Ｒ⁴⁴は、それぞれ独立して、水素原子、炭素数１〜２０の飽和炭化水素基、置換基を有していてもよい炭素数６〜２０の芳香族炭化水素基又は置換基を有していてもよい炭素数７〜３０のアラルキル基を表し、該炭素数１〜２０の飽和炭化水素基において、該飽和炭化水素基に含まれる水素原子は、置換若しくは非置換のアミノ基又はハロゲン原子に置換されていてもよく、該飽和炭化水素基の炭素数が２〜２０である場合、該飽和炭化水素基に含まれるメチレン基は酸素原子又は−ＣＯ−に置換されていてもよい。ただし、該炭素数２〜２０の飽和炭化水素基において、隣接するメチレン基が同時に酸素原子に置換されることはなく、末端のメチレン基が酸素原子又は−ＣＯ−に置換されることはない。Ｒ⁴¹とＲ⁴²とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ⁴³とＲ⁴⁴とが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ｒ⁴⁷〜Ｒ⁵⁴は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、炭素数１〜８のアルキル基を表し、該アルキル基を構成するメチレン基は酸素原子又は−ＣＯ−に置換されていてもよい。Ｒ⁴⁸とＲ⁵²とが互いに結合して、−ＮＨ−、−Ｏ−、−Ｓ−又は−ＳＯ₂−を形成していてもよい。
環Ｔ¹は、置換基を有していてもよい炭素数３〜１０の芳香族複素環を表す。
［Ｙ］^m-は、タングステン、モリブデン、ケイ素、及びリンからなる群より選ばれる少なくとも１つの元素と、酸素とを含有する任意のｍ価のアニオンを表す。
ｍは任意の自然数を表す。
なお、１分子中に下記式で表されるカチオンが複数含まれる場合、それらは同じ構造であっても異なる構造であってもよい。

[In Formula (AI), R ^{41 to} R ⁴⁴ each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted group having 6 to 20 carbon atoms. Represents an aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group is A substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group is an oxygen atom or- It may be substituted with CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and terminal methylene groups are not substituted with oxygen atoms or —CO—. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group is an oxygen atom or —CO—. May be substituted. R ⁴⁸ and R ⁵² may be bonded to each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.
[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen.
m represents an arbitrary natural number.
When a plurality of cations represented by the following formula are contained in one molecule, they may be the same structure or different structures.

［式中、環Ｔ¹、Ｒ⁴¹〜Ｒ⁴⁴及びＲ⁴⁷〜Ｒ⁵⁴は、それぞれ、上記と同義である。］］

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ have the same meanings as described above, respectively. ]]

The aromatic heterocyclic ring of ring T ¹ may be a single ring or a condensed ring.
Examples of the substituent that the aromatic heterocyclic ring of ring T ¹ may have include a halogen atom, a cyano group, an optionally substituted alkyl group having 1 to 20 carbon atoms, and a substituent. Examples thereof include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an amino group which may have a substituent. Ring T ¹ preferably has an amino group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms.
Among them, the aromatic heterocycle of the ring T ¹ is preferably an aromatic heterocycle containing a nitrogen atom, and more preferably a 5-membered aromatic heterocycle containing a nitrogen atom.

Furthermore, the ring T ¹ is particularly preferably a ring represented by the formula (Ab2-y1).

［Ｒ⁵⁶は、水素原子、炭素数１〜２０の飽和炭化水素基、又は置換基を有していてもよい芳香族炭化水素基を表す。
Ｘ２は、酸素原子、−ＮＲ⁵⁷−又は硫黄原子を表す。
Ｒ⁵⁷は、水素原子又は炭素数１〜１０のアルキル基を表す。
Ｒ⁴⁵及びＲ⁴⁶は、互いに独立に、置換基を有していてもよい炭素数１〜２０の飽和炭化水素基、炭素数２〜２０のアルキル基であって、該アルキル基に含まれるメチレン基が酸素原子で置換されていてもよい基、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよいアラルキル基あるいは水素原子を表す。Ｒ⁴⁵とＲ⁴⁶とが結合してそれらが結合する窒素原子とともに環を形成してもよい。
ただし、隣接するメチレン基が同時に酸素原子に置換されることはなく、また、アルキル基の末端のメチレン基が酸素原子に置換されることもない。
＊は、カルボカチオンとの結合手を表す。］

[R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.
X2 represents an oxygen atom, -NR ⁵⁷ - represents a or sulfur atom.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ⁴⁵ and R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may have a substituent, and methylene contained in the alkyl group The group represents a group that may be substituted with an oxygen atom, an aromatic hydrocarbon group that may have a substituent, an aralkyl group that may have a substituent, or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
However, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the methylene group at the terminal of the alkyl group is not substituted with an oxygen atom.
* Represents a bond with a carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ and R ⁵⁶ may be linear, branched or cyclic. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl, icosyl, etc. Linear alkyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and the like. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ^{41 to} R ⁴⁶ and R ⁵⁶ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

The saturated hydrocarbon group for R ^{41 to} R ⁴⁶ and R ⁵⁶ may be substituted with a halogen atom or an optionally substituted amino group. Examples of the optionally substituted amino group include an amino group; an alkylamino group such as a dimethylethylamino group and a diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the halogen atom is a fluorine atom, the halogen atom is preferably substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, or a heptafluoropropyl unit.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ include a linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ and having 1 to 8 carbon atoms. The group of is mentioned.
The alkyl group having 1 to 10 carbon atoms represented by R ^57, 1 to 10 carbon atoms of the saturated hydrocarbon group having a straight chain or branched chain exemplified as saturated hydrocarbon group represented by R ⁴¹ Groups.

When the saturated hydrocarbon group (preferably an alkyl group) represented by R ^{41 to} R ⁴⁶ has 2 or more carbon atoms, the methylene group contained in the saturated hydrocarbon group (preferably an alkyl group) is an oxygen atom or — It may be substituted with CO-, and preferably may be substituted with an oxygen atom. An oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group (preferably an alkyl group). The carbon number of the saturated hydrocarbon group (preferably an alkyl group) is preferably 2 to 10, more preferably 2 to 8. When the methylene group is substituted with an oxygen atom or —CO—, the number of carbon atoms between the terminal and the oxygen atom or —CO— or between the oxygen atom or —CO— and the oxygen atom or —CO— is, for example, 1 to 5, preferably 2 to 3, more preferably 2. However, the adjacent methylene group is not simultaneously substituted with an oxygen atom, and the methylene group at the terminal of the alkyl group is not substituted with an oxygen atom.

Further, R ⁴¹ to R ^46, and as the aromatic hydrocarbon group which may have a substituent represented by R ^56, preferably 6 to 20 carbon atoms, more preferably carbon number 6 to 15 and more preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, preferably a phenyl group, a naphthyl group, a tolyl group, A xylyl group, particularly preferably a phenyl group. The aromatic hydrocarbon group may have one or more substituents, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; chloromethyl group, A haloalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfamoyl group; an alkylsulfonyl having 1 to 6 carbon atoms such as a methylsulfonyl group Group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

As the aralkyl group which may have a substituent represented by R ^{41 to} R ⁴⁶ , a group having 1 to 5 carbon atoms such as a methylene group, an ethylene group or a propylene group may be added to the group described as the aromatic hydrocarbon group. Examples include a group to which an alkanediyl group is bonded.

A ring formed by combining R ⁴¹ and R ⁴² with a nitrogen atom to which they are bonded, a ring formed by combining R ⁴³ and R ⁴⁴ with a nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ Examples of the ring formed together with the nitrogen atom to which they are bonded include nitrogen-containing non-aromatic 4- to 7-membered rings such as pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring, preferably pyrrolidine ring, piperidine ring 4-7 membered ring which has only one nitrogen atom as a hetero atom, such as.

Among them, as R ^{41 to} R ⁴⁴ and R ⁵⁶ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable. A saturated hydrocarbon group of ˜8 or a group represented by the following formula is more preferable. In the following formula, * represents a bond with a nitrogen atom.

R ^{45 to} R ⁴⁶ each independently have a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which an oxygen atom is inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or a substituent. It is preferably an aromatic hydrocarbon group that may be present, or R ⁴⁵ and R ⁴⁶ are bonded to form a ring together with the nitrogen atom to which they are bonded. More preferred embodiments, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, alkylene Koki shea alkyl group, or a group represented by the following formula, or a R ⁴⁵ In this embodiment, R ⁴⁶ is bonded to form a 4- to 7-membered ring having only one nitrogen atom as a hetero atom. In the following formula, * represents a bond with a nitrogen atom.

Examples of the group in which the alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ and the methylene group of the alkyl group having 2 to 8 carbon atoms are substituted with an oxygen atom or —CO— include the above R An example is a group selected from those corresponding to ^{41 to} R ⁴⁶ having 8 or less carbon atoms.

R ^{47 to} R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms from the viewpoint of ease of synthesis, and each independently represents a hydrogen atom or a methyl group. More preferably, they are a fluorine atom or a chlorine atom.

  Examples of the cation moiety of formula (AI) include cation 1 to cation 14 represented by formula (AI-1) as shown in Table 1 below.

  In Table 1, Ph1 to Ph9 mean groups represented by the following formulae. In the formula, * represents a bond.

  Among them, as the cation moiety of the formula (AI), cation 1 to cation 6 and cation 11 to cation 14 are preferable, cation 1, cation 2 or cation 12 to cation 14 are particularly preferable, and most preferable is cation 12 is there.

  Examples of the compound (Aa) include compounds represented by the following formula.

  The compound represented by the formula (AI) can be produced according to the method described in JP-A-2015-28121.

Dye (Ab)
Examples of the dye include compounds classified as those having a hue other than pigments in the color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company). It is done. Particularly preferred are xanthene dyes and azo dyes (for example, monoazo dyes, diazo dyes, triazo dyes, metal complex azo dyes).

  As the xanthene dye, in addition to the compounds exemplified above, for example, C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described), 52, 87, 92, 94, 388, C.I. I. Acid Violet 9, 30C. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Examples thereof also include Reactive Red 36 (Rose Bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, and xanthene dyes described in Japanese Patent No. 4492760.

  The xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter also referred to as compound (a1-1)). The compound (a1-1) may be a tautomer thereof.

［式（ａ１−１）中、Ｒ¹〜Ｒ⁴は、互いに独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基、又は、置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれるメチレン基（−ＣＨ₂−）は、−Ｏ−、−ＣＯ−又は−ＮＲ¹¹−で置き換わっていてもよい。Ｒ¹及びＲ²は、一緒になって窒素原子を含む環を形成してもよく、Ｒ³及びＲ⁴は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上のとき、複数のＲ⁵は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表し、４つのＲ¹¹は同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ⁸−で置き換わっていてもよく、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］

[In formula (a1-1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a methylene group (—CH ₂ —) contained in the saturated hydrocarbon group, —O—, —CO— or It may be replaced by —NR ¹¹ —. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ contained in the saturated hydrocarbon group — May be replaced by —O—, —CO—, —NH— or —NR ⁸ —, wherein R ⁹ and R ¹⁰ are bonded to each other and are a 3- to 10-membered heterocyclic ring containing a nitrogen atom. May be formed.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

  Moreover, as a xanthene dye, the compound (henceforth a "compound (a1-2)") represented by a formula (a1-2) is also preferable. The compound (a1-2) may be a tautomer thereof.

［式（ａ１−２）中、Ｒ²¹及びＲ²²は、互いに独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該Ｒ²¹、Ｒ²²の飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルコキシ基で置換されていてもよく、前記Ｒ²¹、Ｒ²²の飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＣＯ−又は−ＮＲ¹¹−で置き換わっていてもよい。
Ｒ²³及びＲ²⁴は、互いに独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルキルスルファニル基又は炭素数１〜４のアルキルスルホニル基を表す。
Ｒ²¹及びＲ²³は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²²及びＲ²⁴は、一緒になって窒素原子を含む環を形成してもよい。
ｐ及びｑは、互いに独立に、０〜５の整数を表す。ｐが２以上のとき、複数のＲ²³は同一でも異なってもよく、ｑが２以上のとき、複数のＲ²⁴は同一でも異なってもよい。
Ｒ¹¹は、上記と同じ意味を表す。］

[In Formula (a1-2), R ²¹ and R ²² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and are included in the saturated hydrocarbon group of R ²¹ and R ^22. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group is substituted with an alkoxy group having 1 to 3 carbon atoms. And —CH ₂ — contained in the saturated hydrocarbon group of R ²¹ and R ²² may be replaced by —O—, —CO— or —NR ¹¹ —.
R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ²¹ and R ²³ may together form a ring containing a nitrogen atom, and R ²² and R ²⁴ may together form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different.
R ¹¹ represents the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ²¹ and R ²² include those having 1 to 10 carbon atoms among those in R ⁸ .
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the same groups as those in R ¹ .
As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
R ²¹ and R ²² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
R ²³ and R ²⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

  p and q are preferably an integer of 0 to 2, and preferably 1 or 2.

As other dyes, azo dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, quinophthalone dyes and the like may be used, and known dyes are used.
Examples of the azo dye include C.I. I. Direct yellow (hereinafter, description of CI direct yellow is omitted and only the number is described) 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95 98, 102, 109, 129, 136, 141;
C. I. Direct orange 41, 46, 56, 61, 64, 70, 96, 97, 106, 107;
C. I. Direct Red 79, 82, 83, 84, 97, 98, 99, 106, 107, 172, 173, 176, 177, 179, 181, 182, 204, 207, 211, 213, 218, 221, 222, 232, 233, 243, 246, 250;
C. I. Direct violet 47, 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 51, 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101, 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170, 172, 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275;
C. I. Direct green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82, etc .;
C. I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;
C. I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
C. I. Acid Violet 11, 56, 58;
C. I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
C. I. Acid Brown 2, 4, 13, 248;
C. I. Acid Blue 92, 102, 113, 117 etc .;
C. I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46: 1, 82;
C. I. Basic orange 2, 24, 25;
C. I. Basic violet 18;
C. I. Basic yellow 15, 24, 25, 32, 36, 41, 73, 80;
C. I. Basic brown 1;
C. I. Basic blue 41, 54, 64, 66, 67, 129 etc. are mentioned.

The azo dye may be a metal complex azo dye. The metal complex salt azo dye is a compound in which a ligand containing an azo skeleton and a central metal form a complex. As a central metal, chromium, cobalt, and nickel are preferable, and chromium or cobalt is more preferable.
As the metal complex salt azo dye, for example, a compound represented by the following formula (a2-1) (hereinafter also referred to as compound (a2-1)) is more preferable. The compound (a2-1) may be a tautomer thereof.

［式（ａ２−１）中、Ｒ⁷¹〜Ｒ⁸⁸は、それぞれ独立に、水素原子、炭素数１〜８の１価の飽和炭化水素基、ニトロ基、−ＳＯ₂ＮＨＲ⁹¹、−ＳＯ₃Ｈ又は−ＳＯ₂ＣＨ₃を表す。
Ｒ⁸⁹及びＲ⁹⁰は、それぞれ独立に、水素原子、メチル基又はエチル基を表す。
Ｒ⁹¹は、それぞれ独立に、水素原子、炭素数１〜８の１価の飽和炭化水素基、炭素数２〜１５のアルコキシアルキル基を表す。
Ａ¹〜Ａ⁴は、それぞれ独立に、＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−を表す。＊はＭとの結合手を表す。
Ｍは、Ｃｒ又はＣｏを表す。
ｎは、１〜５の整数を表す。
Ｄ⁺は、ヒドロン、又は１価の金属カチオンを表す。］

Wherein (a2-1), R ⁷¹ ~R ⁸⁸ are independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro _{^{group, -SO 2 NHR 91, -SO 3}} H or an -SO ₂ CH _3.
R ⁸⁹ and R ⁹⁰ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ^{1 to} A ⁴ each independently represent * —O—, * —O—CO—, or * —CO—O—. * Represents a bond with M.
M represents Cr or Co.
n represents an integer of 1 to 5.
D ⁺ represents hydrone or a monovalent metal cation. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ^{71 to} R ⁸⁸ and R ⁹¹ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n -Linear alkyl groups such as hexyl group, n-heptyl group, n-octyl group; isopropyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl Groups, branched alkyl groups such as 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and 1,1,5,5-tetramethylhexyl group.
Of R ^{71 to} R ⁸⁸ , at least one is preferably a nitro group. By having a nitro group, the spectral concentration of the compound tends to increase.
R ⁸⁹ and R ⁹⁰ are preferably a methyl group.

Examples of the alkoxyalkyl group having 2 to 15 carbon atoms represented by R ⁹¹ include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a 1-ethoxypropyl group, a 2-ethoxypropyl group, 1-ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2-isopropoxy- Examples include 1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

In the above formula (a2-1), preferred combinations of the groups are as follows.
That is, in the formula (a2-1),
One of R ^{71 to} R ⁷⁹ is a hydrogen atom or a nitro group, one is one selected from a hydrogen atom, SO ₂ NHR ⁹¹ , —SO ₃ H, and —SO ₂ CH ₃ , and the rest is a hydrogen atom And
One of R ^{80 to} R ⁸⁸ is a hydrogen atom or a nitro group, one is one selected from a hydrogen atom, SO ₂ NHR ⁹¹ , —SO ₃ H, and —SO ₂ CH ₃ , and the rest is a hydrogen atom And
R ⁸⁹ and R ⁹⁰ are methyl groups,
R ⁹¹ is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms,
Two of A ^{1 to} A ⁴ are * —O—, and the rest are the same * —O— or * —O—CO—,
M is Cr,
D is Na,
A combination in which n is 1 is preferable.

  Examples of metal complex azo dyes include C.I. I. Solvent Red 125, 130; C.I. I. Examples thereof include Solvent Yellow 21, and compounds described in JP 2010-170116 A or JP 2011-215572 A.

Colored liquid mixture In producing the colored curable resin composition of the present invention, it is preferable that the compound (Aa) is dissolved or dispersed in a solvent and mixed to prepare a colored liquid mixture. By forming a colored curable resin composition by mixing a colored mixed liquid with a resin (B), a polymerizable compound (C), a polymerization initiator (D), and the like, the colored curable resin composition is formed. The heat resistance of the prepared color filter can be further increased.

Any solvent can be used as long as it can be used as the solvent (E) of the colored curable resin composition. The solvent is, for example, an ether ester solvent, more preferably a solvent in which one hydroxy group of alkylene glycol or polyalkylene glycol is etherified and the remaining hydroxy group is esterified, such as propylene glycol monomethyl ether acetate, propylene Examples include glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate. These may be contained alone or in combination.
In the colored mixed solution, the content of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass with respect to 1 part by mass of the compound (Aa).

  In preparing a colored mixed solution by dispersing the compound (Aa) in a solvent, it is preferable to use a dispersant. As the dispersant, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.

  In the colored mixture, the content of the dispersant is, for example, 1 to 1000 parts by weight, preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, with respect to 100 parts by weight of the compound (Aa). Preferably it is 10-30 mass parts.

  The colored mixed solution may contain part or all of the dye (Ab), preferably all in advance. The amount of the dye (Ab) in the colored mixed solution is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts per 100 parts by mass of the compound (Aa). Part by mass.

  When preparing a colored mixed liquid by dispersing the compound (Aa) in a solvent, the colored mixed liquid contains part or all of the resin (B) contained in the colored curable resin composition, preferably partly in advance. You may go out. By including the resin (B) in advance, the dispersion stability when the colored curable resin composition is obtained can be further improved. Content of resin (B) in a colored liquid mixture is 1-300 mass parts with respect to 100 mass parts of compounds (Aa), Preferably it is 10-100 mass parts, More preferably, it is 20-70 mass parts. is there.

  The mass ratio of the dye (Ab) to the compound (Aa) (dye (Ab) / compound (Aa)) is preferably 0.001 or more and 0.5 or less, more preferably 0.005 or more, 0.4 Hereinafter, it is more preferably 0.01 or more and 0.3 or less, still more preferably 0.02 or more and 0.2 or less.

  The colorant (A) may further contain a pigment (Ac) in addition to the compound (Aa) and the dye (Ab). Examples of the pigment include pigments classified as pigments in the color index (published by The Society of Dyers and Colorists) (however, they are different from the compound (Aa)), and the following pigments can be exemplified.

Green pigment: C.I. I. Pigment Green 7, 36, 58, etc. Yellow pigment: C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc. Orange pigment: C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. Red pigment: C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Blue pigment: C . I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, etc. Violet color pigment: C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. As for these pigments, one type of pigment or a plurality of pigments may be used for each color, or pigments of each color may be combined.

  Among these, the pigment (Ac) is preferably a blue pigment or a red pigment, and more preferably C.I. I. Pigment blue 15: 3, 15: 6 or C.I. I. Pigment red 177, 242, 254, 255, 264.

  If necessary, the pigment is atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The pigment particle size is preferably substantially uniform. The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

  Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic, and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, acrylic-based surfactants, and the like. Of these, acrylic surfactants are particularly preferable. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) ) (Manufactured by BASF), Azisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie) and the like.

  When using a pigment dispersant, the amount used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 15 parts by mass or more and 180 parts by mass or less, and still more preferably 20 parts by mass with respect to 100 parts by mass of the pigment. Part to 160 parts by mass. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion having a more uniform dispersion state is obtained when two or more pigments are used.

The content of the colorant (A) in the colored curable resin composition is usually 5% by mass or more and 70% by mass or less, preferably 7% by mass or more and 60% by mass or less, based on the total amount of the solid content. More preferably, it is 10 mass% or more and 55 mass% or less, Most preferably, it is 12 mass% or more and 50 mass% or less. When the content of the compound (Aa) is within the above range, a desired spectrum and color density can be easily obtained. In addition, in this specification, "the total amount of solid content" means the total amount of the component remove | excluding the solvent from the colored curable resin composition of this invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography and gas chromatography, for example.
When the pigment (Ac) is included, the content of the pigment (Ac) is preferably 1% by mass or more and 80% by mass or less, and more preferably 2 parts by mass or more with respect to the total amount of the colorant (A). It is 70 mass% or less, More preferably, it is 5 mass% or more and 60 mass% or less.

<Resin (B)>
The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin and has a structure derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. More preferred are addition polymers having units. Examples of such a resin include the following resins [K1] to [K6].
Resin [K1]: at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a carbon number of 2 to 4 A copolymer of the monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”) Resin [K2]: (a), (b) , (A) copolymerizable monomer (c) (however, different from (a) and (b)) (hereinafter sometimes referred to as “(c)”) Resin [K3 ]: Copolymer of (a) and (c) Resin [K4]: Resin obtained by reacting (b) with copolymer of (a) and (c) Resin [K5]: (b ) And a resin obtained by reacting (a) with a copolymer of (c) Resin [K6]: Copolymerization of (b) and (c) Resin (B) obtained by reacting (a) with carboxylic acid anhydride is at least one monomer selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride A copolymer comprising a structural unit derived from a body and a structural unit derived from a monomer having an ethylenically unsaturated bond and a cyclic ether structure having 2 to 4 carbon atoms, that is, resin [K1] and / or It is preferable that resin [K2] is included.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, Bicyclounsaturated compounds containing a carboxy group such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene, 5-carboxyethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Carboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and anhydrides of unsaturated dicarboxylic acids such as 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; Etc.
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

  (B) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. . (B) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group.

  (B) includes a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a monomer having an oxetanyl group and an ethylenically unsaturated bond. (B2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).

  (B1) may be a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) ) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  (B1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,4 Examples include 6-tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) Acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), represented by Formula (1) And a compound represented by the formula (2).

[Wherein, R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. Each independently X ^a and X ^b, a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]

  The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone, or the compound represented by the formula (1) and the compound represented by the formula (2) May be used in combination. When these are used in combination, the ratio of the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is mol. The standard is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

(B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
(B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.

  (B) is preferably (b1), and the storage stability of the colored curable resin composition is excellent in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. In this respect, (b1) is preferably (b1-2).

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decan-8-yl (meth) acrylate (in this technical field, it is said to be “dicyclopentanyl (meth) acrylate” as a common name. It may also be referred to as “tricyclodecyl (meth) acrylate”) ), Tricyclo [ .2.1.0 ^2,6] (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Decene-8-yl (meth) acrylate, dicyclopentenyl oxyethyl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid ester;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, etc. Unsaturated compounds;
Dicarbonylimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride and vinylidene chloride Halogenated hydrocarbons such as: vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene dienes; .

Among these, a vinyl group-containing aromatic compound, a dicarbonylimide compound, and a bicyclounsaturated compound are preferable from the viewpoints of copolymerization reactivity and heat resistance. Specifically, styrene, vinyl toluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N -Benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

  Resins [K1] to [K3] can be produced, for example, by polymerizing a monomer that leads to the structural unit of the polymer in a solvent in the presence of a polymerization initiator. As a solvent, what dissolve | melts each monomer should just be mentioned, The solvent etc. which are mentioned later are mentioned as a solvent (E) of the colored curable resin composition of this invention.

  Examples of the carboxylic acid anhydride used for the production of the resin [K6] include the acid anhydrides mentioned in (a).

The resin (B) may be used alone or in combination of two or more, and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meta ) Acrylic acid / vinyltoluene copolymer, benzyl (meth) acrylate / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / A resin obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid copolymer is particularly preferable.

When two or more kinds of resins are combined, a combination of resin [K1] and / or resin [K2] and resin [K4] to resin [K6] is preferable, and resin [K1] and / or resin [K2] and resin [K4] are preferable. ] Is more preferable.
When combining the resin [K1] and / or the resin [K2] and the resin [K4] to the resin [K6], the mass ratio ({resin [K1] and / or resin [K2]} / {resin [K4] to The resin [K6]}) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and even more preferably 30/70 to 70/30.

  The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 4,000 to 100,000, and still more preferably 5,000 to 80,000. Even more preferably, it is 6,000 or more and 50,000 or less. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and still more preferably 1.3. ~ 3.

  The acid value (in terms of solid content) of the resin (B) is preferably 20 to 200 mg-KOH / g, more preferably 50 mg-KOH / g or more, still more preferably 80 mg-KOH / g or more, more preferably It is 180 mg-KOH / g or less, More preferably, it is 150 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

  The total content of the resin (B) is preferably 10 to 65% by mass, more preferably 15 to 60% by mass, still more preferably 20 to 60% by mass, and much more based on the total amount of the solid content. Preferably it is 23-55 mass%, Most preferably, it is 25-55 mass%. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and a (meth) acrylic acid ester. Compounds having a structure are preferred. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (A), (b) and (c). Examples of polymerizable compounds having two ethylenically unsaturated bonds include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (Meth) acrylate is mentioned. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (Meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate and capro Ton-modified dipentaerythritol hexa (meth) acrylate.
Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

  Content of the polymeric compound (C) in the colored curable resin composition of this invention is 1-60 mass% normally with respect to the total amount of solid content, Preferably it is 5-50 mass%, More Preferably it is 10-40 mass%, More preferably, it is 12-35 mass%. The content ratio of the resin (B) and the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65, based on mass. ~ 80: 20. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  Examples of O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine And at least one selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, and N-benzoyloxy-1- (4- More preferred is phenylsulfanylphenyl) octane-1-one-2-imine.

  Alkylphenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one And 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

  Alkylphenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, It may be -hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyldimethyl ketal.

  Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6-piperonyl-1,3. 5-triazine is mentioned.

  Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, JP-A-6-75372, and JP-A-6- Examples thereof include compounds described in JP-A-75373, JP-B-48-38403, JP-A-62-174204, and JP-A-07-010913, and compounds represented by the following formulas.

  Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ′. -Benzophenone compounds such as methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- Examples include quinone compounds such as ethyl anthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant described below (particularly an amine polymerization initiation assistant).

  Content of a polymerization initiator (D) is 0.1-40 mass parts normally with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30. It is a mass part, More preferably, it is 1-30 mass parts, Most preferably, it is 1-20 mass parts.

<Polymerization initiation aid>
The polymerization initiation assistant is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiation assistant, it is usually used in combination with a polymerization initiator (D).
Examples of the polymerization initiation assistant include amine polymerization initiation assistants, alkoxyanthracene polymerization initiation assistants, thioxanthone polymerization initiation assistants, and carboxylic acid polymerization initiation assistants.

  Examples of the amine polymerization initiation assistant include alkanolamines such as triethanolamine, methyldiethanolamine, triisopropanolamine; N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4, Examples thereof include 4′-bis (diethylamino) benzophenone and 4,4′-bis (ethylmethylamino) benzophenone. Among them, alkylaminobenzophenone such as 4,4′-bis (diethylamino) benzophenone is preferable. Among these, alkylaminobenzophenone is preferable, and 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  As an alkoxyanthracene polymerization initiation assistant, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, Examples include 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the thioxanthone polymerization initiation assistant include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Examples of the carboxylic acid polymerization initiation assistant include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid and N-phenylglycine.

  When using a polymerization initiation aid, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiation assistant is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>
Solvent (E) comprises a solvent k of n species, and S value 8.75 obtained by the following equation (cal / cm ^{3) 1/2} ultra 11.11 (cal / cm ³⁾ is less than ^1/2 is there. For details of the Fedors method, see Polymer Engineering and Science, 1974, vol. 14, p. 147-154.

［式（１）中、ａ_kは、全溶剤に対する溶剤ｋの含有率を表す。
ｂ_kは、Ｆｅｄｏｒｓ法に基づく溶剤ｋのＳＰ値を表す。
ｎは、１以上の整数を表す。］

[In formula (1), _ak represents the content rate of the solvent k with respect to all the solvents.
b _k represents the SP value of the solvent k based on the Fedors method.
n represents an integer of 1 or more. ]

When the solvent is one kind (n = 1), the SP value of the solvent 1 becomes the S value as it is.
When the number of solvents is two (n = 2), the content a _{1 of} the solvent 1 with respect to the total solvent and the content a ₂ of the solvent 2 with respect to the total solvent are obtained with respect to the total amount of the solvent 1 and the solvent 2, respectively S value = (Solvent 1 content a ₁ × Solvent 1 SP value) + (Solvent 2 content a ₂ × Solvent 2 SP value).
n is preferably 2 or more, more preferably an integer of 2 to 5, and further preferably 2 or 3.

The S value is more than 8.75 (cal / cm ³ ) ^1/2 and less than 11.11 (cal / cm ³ ) ^1/2 , preferably 8.76 (cal / cm ³ ) ^1/2 or more. 00 (cal / cm ³ ) ^1/2 or less, more preferably 8.77 (cal / cm ³ ) ^1/2 or more and 10.90 (cal / cm ³ ) ^1/2 or less, more preferably 10.80 (cal / Cm ³ ) ^1/2 or less, even more preferably 10.70 (cal / cm ³ ) ^1/2 or less, particularly preferably 10.60 (cal / cm ³ ) ^1/2 or less, most preferably 10.50. (Cal / cm ³ ) ^1/2 or less. When the above range is not satisfied, the brightness is lowered, the dissolution time of the colored composition layer is prolonged, and the storage stability tends to be deteriorated.

  A solvent (E) is not limited, The solvent normally used in the said field | area can be used individually or in combination of 2 or more types. Specifically, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O -, -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

  Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, pyruvin Examples include methyl acid, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol butyl ether, dipropylene glycol methyl propyl ether, tripropylene glycol monomethyl ether , Tripropylene glycol butyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl Examples include ether, diethylene glycol dibutyl ether, anisole, phenetole and methylanisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, propylene glycol diacetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Is mentioned.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

  Two or more of these solvents may be combined.

  Among the above solvents, an organic solvent having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, N, N-dimethylformamide and N-methylpyrrolidone are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene Glycol monobutyl ether, dipropylene glycol methyl ether Acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N, N-dimethylformamide and N-methylpyrrolidone, 4-hydroxy-4-methyl-2-pentanone, Propylene glycol diacetate is more preferred.

The solvent (E) is one or more selected from a first solvent having an SP value of less than 9.0 (cal / cm ³ ) ^1/2 and an SP value of 9.0 (cal / cm ³ ) ^1/2 or more. Preferably, the solvent (E) is selected from one or more selected from a third solvent having a boiling point of less than 150 ° C and a fourth solvent having a boiling point of not less than 150 ° C. It is preferable that 1 or more types are included. The SP value can be calculated by the Fedors method.
The solvent (E) may preferably contain a solvent (i) belonging to either the first solvent or the third solvent, and a solvent (ii) belonging to any of the second solvent or the fourth solvent, More preferably, the solvent (i) belonging to both the first solvent and the third solvent and the solvent (ii) belonging to both the second solvent and the fourth solvent may be included. The solvent (E) may contain a solvent (i) belonging to both the first solvent and the third solvent, and a solvent (ii) belonging to both the second solvent and the third solvent.
As long as the S value is satisfied, the solvent (i) may contain a solvent belonging to either the first solvent or the third solvent, and the solvent (ii) includes the second solvent and the fourth solvent. The solvent which belongs to either of these may be contained.
Among them, the solvent (i) belonging to both the first solvent and the third solvent is preferably an ether solvent, more preferably an ether solvent having an alkylene glycol, and further preferably propylene glycol monomethyl ether acetate (boiling point). 146 ° C .: SP value 8.73 (cal / cm ³ ) ^1/2 ).
The solvent (ii) belonging to both the second solvent and the fourth solvent is preferably selected from an ester solvent, an ether solvent, and a ketone solvent, an ester solvent having an alkyl group, an ether solvent having an alkylene glycol, a hydroxy group More preferred is a ketone solvent having an ethyl lactate (boiling point 155 ° C .: SP value 11.93 (cal / cm ³ ) ^1/2 ), propylene glycol diacetate (boiling point 190 ° C .: SP value 9.60 (cal / Cm ³ ) ^1/2 ), 4-hydroxy-4-methyl-2-pentanone (boiling point 168 ° C .: SP value 11.70 (cal / cm ³ ) ^1/2 ) is more preferable.
Furthermore, the solvent (ii) belonging to both the second solvent and the third solvent is preferably an ether solvent, more preferably an ether solvent having an alkylene glycol, and propylene glycol monomethyl ether (boiling point 120 ° C .: SP More preferably, the value 11.27 (cal / cm ³ ) ^1/2 ).

  The first solvent (preferably a solvent satisfying both the first solvent and the third solvent) is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more, in 100% by mass of the total solvent. For example, it is 99% by mass or less, preferably 98% by mass or less, more preferably 97% by mass or less, and still more preferably 95% by mass or less. When the first solvent does not satisfy the above range, the brightness of the obtained color filter is lowered, the dissolution time of the colored composition layer is lengthened, and the storage stability tends to deteriorate.

  Content of a solvent (E) is 60-95 mass% normally with respect to the total amount of colored curable resin composition, Preferably it is 65-92 mass%, More preferably, it is 70-90 mass%. . When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<Leveling agent>
The colored curable resin composition may contain a leveling agent. Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

  Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) are listed.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) can be mentioned.

The content of the leveling agent is usually 0.0005% by mass or more and 0.6% by mass or less, preferably 0.001% by mass or more and 0.5% by mass or less, based on the total amount of the colored curable resin composition. More preferably 0.001% by mass to 0.2% by mass, still more preferably 0.002% by mass to 0.1% by mass, and particularly preferably 0.005% by mass to 0.07% by mass. It is below mass%. When the leveling agent content is within the above range, the flatness of the color filter can be improved.
The content of the leveling agent is usually from 0.001% by mass to 2.0% by mass, preferably from 0.002% by mass to 1.5% by mass, based on the total solid content of the colored curable resin composition. Or less, more preferably 0.004 to 1.0% by mass, still more preferably 0.008 to 0.5% by mass, particularly preferably 0.01 to 0% by mass. .3% by mass or less.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and, if necessary, It can be prepared by mixing a leveling agent, a polymerization initiation aid and other components.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed can be used as the color filter of the present invention.

  The film thickness of the color filter to be produced can be appropriately adjusted according to the purpose and application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.

  As the substrate, a glass plate, a resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

  The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.

  First, a colored curable resin composition is applied on a substrate, dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained. Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method.

  Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. Use an exposure device such as a mask aligner or stepper because it can irradiate parallel light uniformly over the entire exposure surface and perform precise alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred. A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide. The development method may be any of paddle method, dipping method and spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

  It is preferable to further post-bake the resulting colored pattern. The color filter having a colored pattern or a colored coating film thus obtained may be further subjected to surface coating treatment in order to impart various characteristics.

  The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

Synthesis example 1
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, and then stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

  The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer is charged with 8.2 parts of the compound represented by the formula (BI-7), 10 parts of the compound represented by the formula (CI-18) and 20 parts of toluene. Then, 12.2 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction solution was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were added, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Next, after adding 396 parts of water to the blue solution, the mixture was further stirred at room temperature for 30 minutes to obtain a reaction solution.
A beaker is charged with 53 parts of water, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol are poured into the water and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. Prepared.
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 17.1 parts of a compound represented by the formula (AI-18).

Synthesis example 2
20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was 110 ° C For 6 hours. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 800 parts of water and 50 parts of 35% by weight hydrochloric acid and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain a compound represented by the formula (1-32).

Synthesis example 3
After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-4-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of a 35% aqueous sodium nitrite solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve, followed by stirring for 2 hours. A suspension containing was obtained. Subsequently, an aqueous solution in which 5.6 parts of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added to inactivate excess sodium nitrite.
Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) is suspended in 70 parts of water, and the pH is adjusted to 8.0 using sodium hydroxide. did. The suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.7 parts (yield 87%) of the compound represented by the formula (p-2).

  10 parts of the compound of formula (p-2) are dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and ammonium chromium (III) sulfate (III) 12 water (manufactured by Wako Pure Chemical Industries, Ltd.) 3.1. After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to reflux for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% brine, the reddish orange solid obtained after filtration was dried at 60 ° C., and 13.6 parts of the compound represented by formula (z-2) ( Yield 63%) was obtained.

Synthesis example 4
A suitable amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Then 54 parts acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxy tricyclo [5.2.1.0 ^{2, 6} ] A mixed solution prepared by dissolving 225 parts of a mixture of decane-9-yl acrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyltoluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate. Was dropped into the flask over 4 hours.
On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion | finish of dripping of an initiator solution, after hold | maintaining at 85 degreeC for 4 hours, it cooled to room temperature and obtained the copolymer (resin B-1) solution. The solid content of the resin (B-1) solution was 37.5%, and the viscosity measured with a B-type viscometer (23 ° C.) was 246 mPa · s. The weight average molecular weight of the resin (B-1) was 1.06 × 10 ⁴ , the acid value in terms of solid content was 115 mg-KOH / g, and the molecular weight distribution was 2.01. Resin (B-1) has the following structural units.

Synthesis example 5
353 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. After raising the temperature of the solution in the flask to 100 ° C., 18.7 g (0.10 mol) of N-benzylmaleimide, 70.5 g (0.40 mol) of benzyl methacrylate, 51.7 g (0.6 mol) of methacrylic acid. , 90.0 g (0.9 mol) of methyl methacrylate, 5.2 g of azobisisobutyronitrile and 182 g of propylene glycol monomethyl ether acetate were dropped into the flask using a dropping funnel over 2 hours, and dropped. After completion, the mixture was further stirred at 100 ° C. for 5 hours.
After completion of the stirring, air was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with air. Then, 28.5 g of glycidyl methacrylate [0.2 mol (mole fraction relative to methacrylic acid used in this reaction) 33 mol%)), 1.3 g of trisdimethylaminomethylphenol and 0.165 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours. The solid content was 39.3% and the solid content acid value was 80 mg KOH. / G of resin (B-2) solution was obtained. The weight average molecular weight in terms of polystyrene of the obtained resin (B-2) was 16,000.

Synthesis Example 6
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., Benzyl methacrylate 61.7 g (0.35 mol), methacrylic acid 43.0 g (0.5 mol), tricyclodecane skeleton monomethacrylate (Hitachi Chemical Co., Ltd. FA-513M) 33.0 g (0.15 mol) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask from the dropping funnel over 2 hours, and further stirring at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin (B-3) having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 12,000, and the molecular weight distribution (Mw / Mn) was 2.1.

About the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the said resin polymer, it carried out on condition of the following using GPC method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Test solution concentration: 25 mg / mL (solvent: THF)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and number average molecular weight obtained in the above-mentioned manner was defined as the molecular weight distribution (Mw / Mn).

Examples 1 to 21 and Comparative Examples 1 and 2
Each component was mixed so that it might become a composition shown in Tables 4-5, and the colored curable resin composition was obtained. Moreover, S value calculated | required from Formula (1) about the solvent used in Examples 1-21 and Comparative Examples 1 and 2, respectively is shown below.

¹⁾Ａ１−１は、必要に応じて用いる分散剤、Ｂ−１⁴⁾、及びＥ−１⁵⁾欄記載の量のプロピレングリコールモノメチルエーテルアセテートを混合し、予め分散させて使用するか、Ｂ−１⁴⁾、及びＥ−５¹²⁾欄記載の量のプロピレングリコールモノメチルエーテルを混合し、予め分散させて使用する。
²⁾樹脂Ｂ−１含有量の合計を示す。
³⁾プロピレングリコールモノメチルエーテルアセテート含有量の合計を示す。
⁶⁾Ａ１−２は、アクリル系顔料分散剤、Ｂ−１¹⁰⁾、及びＥ−１¹¹⁾欄記載の量のプロピレングリコールモノメチルエーテルアセテートを混合し、予め分散させて使用する。
⁷⁾Ａ１−３は、アクリル系顔料分散剤、Ｂ−１¹⁰⁾、及びＥ−１¹¹⁾欄記載の量のプロピレングリコールモノメチルエーテルアセテートを混合し、予め分散させて使用する。
⁸⁾Ａ１−４は、分散剤、Ｂ−１⁴⁾、及びＥ−１⁵⁾欄記載の量のプロピレングリコールモノメチルエーテルアセテートを混合し、予め分散させて使用する。
⁹⁾Ａ１−５は、分散剤、Ｂ−１⁴⁾、及びＥ−１⁵⁾欄記載の量のプロピレングリコールモノメチルエーテルアセテートを混合し、予め分散させて使用する。

¹⁾ A1-1 is a dispersant used as required, B-14 ⁾ , and propylene glycol monomethyl ether acetate in the amount described in the column E- ¹⁵⁾ are mixed and used in advance, or B -14 ⁾ , and E-5 The amount of propylene glycol monomethyl ether described in the column ¹²⁾ is mixed and dispersed before use.
²⁾ The total resin B-1 content is shown.
³⁾ Indicates the total content of propylene glycol monomethyl ether acetate.
⁶⁾ A1-2 is an acrylic pigment dispersant, B-1 ¹⁰⁾ , and propylene glycol monomethyl ether acetate in the amounts described in the column E- ^{11 11)} are mixed and used in advance.
⁷⁾ A1-3 is an acrylic pigment dispersant, B-1 ¹⁰⁾ , and propylene glycol monomethyl ether acetate in the amount described in the column E- ^{11 11)} are mixed and used in advance.
⁸⁾ A1-4 is used by mixing the dispersant, B-14 ⁾ , and the amount of propylene glycol monomethyl ether acetate described in the column E- ¹⁵⁾ and dispersing them in advance.
⁹⁾ A1-5 is a dispersant, B-14 ⁾ , and E-15 mixed with propylene glycol monomethyl ether acetate in the amounts described in the column ⁵⁾ and used in a predispersed state.

In Tables 4 to 5, each component represents the following. Moreover, resin (B) showed the mass part of solid content conversion.
Colorant (A); 1-1; Compound colorant represented by formula (1-32) (A); 1-2; Compound colorant represented by formula (z-2) (A); A1- 1; Compound colorant represented by formula (AI-18) (A); A1-2; I. Pigment Blue 15: 6
Colorant (A); A1-3; C.I. I. Pigment Red 254
Colorant (A); A1-4; C.I. I. Pigment Blue 1
Colorant (A); A1-5; C.I. I. Pigment Red 81
Resin (B); (B-1); Resin (B-1)
Resin (B); (B-2); Resin (B-2)
Resin (B); (B-3); Resin (B-3)
Polymerizable compound (C); (C-1); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; oxime compound)
Solvent (E); (E-1); Propylene glycol monomethyl ether acetate solvent (E); (E-2); Ethyl lactate solvent (E); (E-3); Propylene glycol diacetate solvent (E); 4-hydroxy-4-methyl-2-pentanone solvent (E); (E-5); propylene glycol monomethyl ether surfactant (F); (F-1); polyether-modified silicone oil ( Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Preparation of colored pattern>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 80 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 35 mJ / The colored composition layer was irradiated with light at an exposure amount of cm ² (based on 365 nm). A photomask having a 50 μm line and space pattern was used. The substrate on which the colored composition layer after light irradiation was formed was added to a developer (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction) at 25 ° C. at 60 ° C. After immersion and development for 2 seconds, washing with water and post-baking at 230 ° C. for 30 minutes in an oven, a colored pattern was obtained.

<Film thickness measurement>
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Tables 6-7.

<Chromaticity evaluation>
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and brightness Y were measured. The results are shown in Tables 6-7.

<Solubility evaluation>
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and ethanol and then dried. A colored curable resin composition was spin-coated on this glass substrate, and then pre-baked at 100 ° C. for 3 minutes in a clean oven to form a colored composition layer.
Next, the substrate on which the colored composition layer has been formed is immersed in a developer at a liquid temperature of 25 ° C. (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction). The time when the 10 mm portion from the center of the substrate was completely dissolved was defined as the dissolution time. If the dissolution time is 25 seconds or less, the solubility is good. Such a colored curable resin composition can be said to be highly productive because it can produce a colored pattern in which development defects such as residues are suppressed even if the development time is short. The results are shown in Tables 6-7.

<Storage stability>
The viscosity of the colored curable resin composition was measured using a viscometer (model: VISCMETER TV-30; manufactured by Toki Sangyo Co., Ltd .; rotational speed: 100 rpm; measurement temperature: 23 ° C.). After the colored curable composition was stored at 40 ° C. for 7 days, the viscosity was measured, and the thickening rate was calculated according to the following formula. The results are shown in Tables 6-7.
Thickening rate = (viscosity after 7 days storage) / (viscosity immediately after preparation)

  The colored curable resin composition of the present invention has good storage stability.

Claims (5)

Containing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E);
The colorant (A) contains a compound and a dye comprising an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen, and a cation having a pigment skeleton,
The solvent (E) contains n kinds of solvents k, and the S value obtained from the formula (1) is more than 8.75 (cal / cm ³ ) ^{1/2 and} 11.11 (cal / cm ³ ) ^1/2 Colored curable resin composition characterized by being less than.

[In formula (1), _ak represents the content rate of the solvent k with respect to all the solvents.
b _k represents the SP value of the solvent k based on the Fedors method.
n represents an integer of 1 or more. ] The solvent (E) is one or more selected from a first solvent having an SP value of less than 9.0 (cal / cm ³ ) ^1/2 and an SP value of 9.0 (cal / cm ³ ) ^1/2 or more The colored curable resin composition of Claim 1 containing 1 or more types selected from the 2nd solvent.   The colored curing according to claim 1 or 2, wherein the solvent (E) contains one or more selected from a third solvent having a boiling point of less than 150 ° C and one or more selected from a fourth solvent having a boiling point of 150 ° C or more. Resin composition.   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 4.