JP6868348B2 - Manufacturing method of color curable resin composition and color filter - Google Patents

Description

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

The color curable resin composition is 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 color-curable resin composition, a color-curable resin composition containing 4-hydroxy-4-methyl-2-pentanone and propylene glycol monomethyl ether acetate (mass ratio 8: 2) as a solvent (patented). A colored curable resin composition containing only Document 1) and propylene glycol monomethyl ether acetate (Patent Document 2) is known.

Japanese Unexamined Patent Publication No. 2015-28121 Japanese Unexamined Patent Publication No. 2014-153570

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] A colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E) are contained, and the colorant (A) is tungsten, molybdenum, silicon and phosphorus. It contains a compound and a dye composed of an anion of a compound containing at least one element selected from the group consisting of oxygen and an oxygen, and a cation having a pigment skeleton, and the solvent (E) contains n kinds of solvents k. 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 the formula (1), a _k represents the content of the solvent k with respect to the total solvent.
b _k represents the SP value of the solvent k based on the Fedors method.
n represents an integer of 1 or more. ]
[2] One or more solvents (E) ^{selected from the 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 /} The colored curable resin composition according to [1], which comprises one or more selected from ^{two or more second solvents.}
[3] 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 higher [1] or [2]. The colored curable resin composition according to.
[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, it is possible to provide a colored curable resin composition having good storage stability.

The color 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) is 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) consisting of a cation having a pigment skeleton, 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 “Aa”). It may be referred to as compound (Aa)) and dye (Ab). The compound (Aa) and the dye (Ab) may be each one or more.

The pigment skeleton in the present invention refers to a partial structure of a compound that selectively absorbs visible light (wavelength; 400 to 750 nm) and has a unique color, and the partial structure is characterized by having a unique color. It contains a structure for expressing.

The pigment skeleton of the cation constituting the compound (Aa) includes an azo skeleton, a xanthene skeleton, an azine skeleton, a cyanine skeleton, an acridine skeleton, an anthraquinone skeleton, a squarylium skeleton, and the like, which have an onium structure; Examples thereof include a dye skeleton in which one or more of the aromatic hydrocarbon rings of the triarylmethane skeleton are aromatic heterocycles. Among them, it is preferably a dye skeleton in which one or more of the aromatic hydrocarbon rings of the xanthene skeleton, the triarylmethane skeleton, and the triarylmethane skeleton are aromatic heterocycles, and more preferably the aromatic hydrocarbon of the triarylmethane skeleton. It is a pigment 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. , Phosphonic acid anion, silicate anion and tungsten-based isopolyacid anion are more preferable.

Examples of the tungsten-containing heteropolyacid anion and isopolyacid anion include kegin-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- , Kegin-type heteropolymetalate 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 can be mentioned.

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 the formula (AI), R ^{41 to} R ⁴⁴ each independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and a substituent having 6 to 20 carbon atoms which may have a substituent. It represents an aralkyl group having 7 to 30 carbon atoms which may have an aromatic hydrocarbon group or a substituent, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group , Substituent or unsubstituted, may be substituted with an 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 replaced with CO−. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom 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 independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, and an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group is an oxygen atom or -CO-. It may be replaced with. R ⁴⁸ and R ⁵² may be combined with 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 oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus.
m represents an arbitrary natural number.
When a plurality of cations represented by the following formulas are contained in one molecule, they may have 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。］］

[In the formula, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ are synonymous with the above, respectively. ]]

The aromatic heterocycle of ring T ¹ may be a monocyclic ring or a condensed ring.
The substituents that the aromatic heterocycle of ring T ¹ may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms that may have a substituent, 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, an aromatic heterocyclic ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably an aromatic heterocyclic 5-membered ring containing a nitrogen atom.

Further, 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 an aromatic hydrocarbon group which may have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or 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 saturated hydrocarbon groups having 1 to 20 carbon atoms and alkyl groups having 2 to 20 carbon atoms, which may have substituents independently of each other, and methylene contained in the alkyl groups. It represents a group whose group may be substituted with an oxygen atom, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring with the nitrogen atom to which they are bonded.
However, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the methylene group at the end of the alkyl group is not replaced with an oxygen atom.
* Represents a bond with a carbocation. ]

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

The cyclic saturated hydrocarbon groups 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, an adamantyl group and the like. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

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

The alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ has 1 to 8 carbon atoms among the saturated hydrocarbon groups of the straight chain or the branched chain exemplified as the saturated hydrocarbon group represented by ^{R 41.} The basis of is mentioned.
Further, as the alkyl group having 1 to 10 carbon atoms represented by ^{R 57} , among the saturated hydrocarbon groups of the linear or branched chains exemplified as the saturated hydrocarbon group represented by ^{R 41, the alkyl group having 1 to 10 carbon atoms} The group is mentioned.

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−, preferably with an oxygen atom. Further, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group (preferably an alkyl group). The saturated hydrocarbon group (preferably an alkyl group) has a preferable carbon number of 2 to 10, more preferably 2 to 8. When the methylene group is replaced 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, , 1-5, preferably 2-3, more preferably 2. However, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the methylene group at the end of the alkyl group is not replaced with an oxygen atom.

The ^{aromatic hydrocarbon group which may have a substituent represented by R 41 to} R ⁴⁶ and R ⁵⁶ preferably has 6 to 20 carbon atoms, and more preferably 6 to 20 carbon atoms. It is 15, more preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group and the like, and preferably a phenyl group, a naphthyl group, a tolyl group and the like. It is a xsilyl group, particularly preferably a phenyl group. Further, the aromatic hydrocarbon group may have one or more substituents, and the substituents 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 group 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 , the group described as the above aromatic hydrocarbon group has 1 to 5 carbon atoms such as a methylene group, an ethylene group and a propylene group. Examples thereof include a group to which an alcandiyl group is bonded.

The ^{rings formed by the bonds of R 41} and R ⁴² with the nitrogen atoms to which they are bonded, the rings formed by the bonds of R ⁴³ and R ⁴⁴ with the nitrogen atoms to which they are bonded, and the rings R ⁴⁵ and R ⁴⁶ are formed. Examples of the ring formed by binding and forming together with the nitrogen atom to which they are bonded include a nitrogen-containing non-aromatic 4- to 7-membered ring such as a pyrrolidine ring, a morpholin ring, a piperidine ring, and a piperazine ring, preferably a pyrrolidine ring and a piperidine ring. Examples of such heteroatoms include 4- to 7-membered rings having only one nitrogen atom.

Among them, as R ^{41 to} R ⁴⁴ and R ⁵⁶ , aromatic hydrocarbon groups having 1 to 20 carbon atoms or which may have a saturated hydrocarbon group or a substituent are preferable, and each of them has 1 carbon number independently. More preferably, it is a saturated hydrocarbon group of ~ 8 or a group represented by the following formula. 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 which may be present, or R ⁴⁵ and R ⁴⁶ are preferably bonded to form a ring with the nitrogen atom to which they are bonded. In a more preferable embodiment, R ^{45 to} R ⁴⁶ are independently saturated hydrocarbon groups having 1 to 8 carbon atoms, an alkyloxyalkyl group, or a group represented by the following formula, or R ⁴⁵ . This ^{is an embodiment in which 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.

Further, as 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−, the above-mentioned R An example is an example in which a group having 8 or less carbon atoms is selected from the corresponding groups of ^{41 to} R ^46.

From ^{the viewpoint of ease of synthesis, R 47 to} R ⁵⁴ are preferably hydrogen atoms, halogen atoms or alkyl groups having 1 to 8 carbon atoms independently of each other, and independently hydrogen atoms and methyl groups, respectively. , Fluorine atom or chlorine atom is more preferable.

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

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

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

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

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 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 (Dyeing Co., Ltd.). Be done. In particular, xanthene dyes and azo dyes (for example, monoazo dyes, diazo dyes, triazo dyes, metal complex salt azo dyes, etc.) are preferable.

Examples of the xanthene dye include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to the others), 52, 87, 92, 94, 388, C.I. I. Acid Violet 9, 30 C.I. 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. Modant Red 27, C.I. I. Examples thereof include reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, 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)). 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 the formula (a1-1), R ^{1 to} R ⁴ are monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms or substituents which may have hydrogen atoms and substituents independently of each other. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have, and the methylene group (−CH ₂₋ ) contained in the saturated hydrocarbon group is −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 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms independently of each other.
m represents an integer from 0 to 5. when m is 2 or more, plural R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ^{+ _{is, + N (R 11) 4}} , represents Na ⁺ or K ^+, 4 one 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 represent monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and are contained in the saturated hydrocarbon groups -CH _2. - is -O -, - CO -, - NH- or -NR ⁸ - may be replaced by, R ⁹ and R ¹⁰ are bonded 3- to 10-membered ring containing a nitrogen atom of each other heterocyclic 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. ]

Further, as the xanthene dye, a compound represented by the formula (a1-2) (hereinafter, may be referred to as “compound (a1-2)”) is also preferable. 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 the formula (a1-2), R ²¹ and R ²² represent monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms independently of each other, and are contained in the saturated hydrocarbon groups 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. even well, the -CH ₂ - contained in the saturated hydrocarbon group R ^21, R ²² - is, -O -, - CO- or -NR ¹¹ - it may be replaced by.
R ²³ and R ²⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl sulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ²¹ and R ²³ may be combined to form a ring containing a nitrogen atom, and R ²² and R ²⁴ may be combined to form a ring containing a nitrogen atom.
p and q represent integers 0 to 5 independently of each other. When p is 2 or more, the plurality of R ^23s may be the same or different, and when q is 2 or more, the plurality of R ^24s may be the same or different.
R ¹¹ has the same meaning as above. ]

Examples of monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms in R ²¹ and R ²² include groups having 1 to 10 carbon atoms among those ^{in R 8.}
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that may have as a substituent include the same group ^{as that in R 1.}
Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like.
R ²¹ and R ²² are preferably monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms independently of each other.

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, a tert-butyl group and the like.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methyl sulfanyl group, an ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group, an isopropyl sulfanyl group and the like.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include a methyl sulfonyl group, an ethyl sulfonyl group, a propyl sulfonyl group, a butyl sulfonyl group and an isopropyl sulfonyl 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 integers of 0 to 2, 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, the 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 and the like can be mentioned.

The azo dye may be a metal complex salt 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 the central metal, chromium, cobalt and nickel are preferable, and chromium or cobalt is more preferable.
The metal complex salt azo dye is more preferably, for example, a compound represented by the following formula (a2-1) (hereinafter, also referred to as compound (a2-1)). 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。］

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

The ^{monovalent saturated hydrocarbon groups 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 and 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 Examples thereof include a branched alkyl group such as a group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group, a 2-ethylhexyl group and a 1,1,5,5-tetramethylhexyl group.
It is preferable that at least one of R ^{71 to} R ^{88 is a nitro group.} Having a nitro group tends to increase the spectral concentration of the compound.
R ⁸⁹ and R ⁹⁰ are preferably methyl groups.

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 and 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 thereof include 1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group and 3- (2-ethylhexyloxy) propyl group.

In the above formula (a2-1), the preferred combination of each group is as follows.
That is, in the equation (a2-1),
One of R ^{71 to} R ⁷⁹ is a hydrogen atom or a nitro group, one is 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 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 and
D is Na
A combination in which n is 1 is preferable.

Examples of the metal complex salt azo dye include C.I. I. Solvent Red 125, 130; C.I. I. Examples thereof include Solvent Yellow 21, and compounds described in JP-A-2010-170116 or JP-A-2011-215772.

Coloring Mixture Solution In producing the color 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 color mixture solution. Formed from the colored curable resin composition by preparing a colored curable resin composition by mixing the colored mixed solution with the resin (B), the polymerizable compound (C), the polymerization initiator (D) and the like. The heat resistance of the plasticized color filter can be further improved.

As the solvent, any solvent that can be used as the solvent (E) of the colored curable resin composition can be used. The solvent is, for example, an ether ester solvent, more preferably a solvent in which one hydroxy group of an alkylene glycol or a polyalkylene glycol is etherified and the remaining hydroxy groups are esterified, for example, propylene glycol monomethyl ether acetate, propylene. Examples thereof 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 used alone or in combination of two or more.
The content of the solvent in the coloring mixture 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).

When the compound (Aa) is dispersed in a solvent to prepare a colored mixed solution, 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 pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Kagaku Co., Ltd.), Solspers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), Ajinomoto Fine (Ajinomoto Fine) Examples thereof include Techno Co., Ltd. and Disperbyk (manufactured by Big Chemie).

The content of the dispersant in the coloring mixture is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, particularly based on 100 parts by mass of the compound (Aa). It is preferably 10 to 30 parts by mass.

The coloring mixture may contain a part or all, preferably all of the dye (Ab) in advance. The amount of the dye (Ab) in the coloring mixture 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 by mass with respect to 100 parts by mass of the compound (Aa). It is a mass part.

When the compound (Aa) is dispersed in a solvent to prepare a colored mixed solution, the colored mixed solution contains a part or all, preferably a part of the resin (B) contained in the colored curable resin composition in advance. You may be. By including the resin (B) in advance, the dispersion stability of the colored curable resin composition can be further improved. The content of the resin (B) in the coloring mixture is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the compound (Aa). 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, and more preferably 0.005 or more and 0.4. Below, it is more preferably 0.01 or more and 0.3 or less, and even 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 by the Color Index (The Society of Dyers and Colorists Publishing) (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. These pigments may use one pigment or a plurality of pigments for each color, or may combine pigments of each color.

Among them, 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 treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, and atomization by a sulfuric acid atomization method or the like. Treatment, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed. The particle size of the pigment is preferably substantially uniform. The pigment can be made into a pigment dispersion liquid in a state of being uniformly dispersed in the pigment dispersant solution by containing a pigment dispersant and performing a dispersion treatment. The pigments may be individually dispersed 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 thereof include polyester-based, polyamine-based, and acrylic-based surfactants. Of these, acrylic surfactants are particularly preferable. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) ) (BASF), Ajisper (registered trademark) (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (Big Chemie) and the like.

When a pigment dispersant is used, 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 further preferably 20 parts by mass with respect to 100 parts by mass of the pigment. More than 160 parts by mass or less. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a more uniform dispersed state tends to be obtained when two or more kinds of pigments are used.

The content of the colorant (A) in the color 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 solids. , More preferably 10% by mass or more and 55% by mass or less, and particularly preferably 12% by mass or more and 50% by mass or less. When the content of the compound (Aa) is within the above range, it becomes easier to obtain the desired spectroscopy and color density. In addition, in this specification, "the total amount of solids" means the total amount of the components excluding the solvent from the color curable resin composition of this invention. The total amount of the solid content and the content of each component relative to the total amount of the solid content can be measured by a known analytical means such as liquid chromatography and gas chromatography.
When the pigment (Ac) is contained, the content of the pigment (Ac) is preferably 1% by mass or more and 80% by mass or less, more preferably 2 parts by mass or more, based on the total amount of the colorant (A). It is 70% by mass or less, more preferably 5% by mass or more and 60% by 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. An addition polymer having a unit is more preferable. 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 unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and 2 to 4 carbon atoms. Copolymer resin [K2]: (a) and (b) with a monomer (b) having an ethylenically unsaturated bond and a cyclic ether structure of , (A) and a copolymer resin [K3] with a copolymerizable monomer (c) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"). ]: Copolymer resin of (a) and (c) Resin [K4]: Resin resin [K5]: (b) obtained by reacting the copolymer of (a) and (c) with (b). Resin obtained by reacting the copolymer of () and (c) with (a) Resin [K6]: Reacting (a) with the copolymer of (b) and (c), and further carboxylic acid Resin obtained by reacting an anhydride The resin (B) has a structural unit derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and ethylenically non-ethyleney. It is preferable to contain a copolymer containing a structural unit derived from a monomer having a saturated bond and a cyclic ether structure having 2 to 4 carbon atoms, that is, a resin [K1] and / or a resin [K2].

As (a), for example, 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-cyclohexendicarboxylic 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 carboxy groups such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 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- Caroxyan anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and unsaturated dicarboxylic acid anhydrides such as 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; And so on.
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylate.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained 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 oxylan ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. .. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of (b) include a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a monomer having an oxetanyl group and an ethylenically unsaturated bond. Examples thereof include (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)”).

The (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 an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter, may be referred to as “(b1-2)”).

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and 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 ( Glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2, 4,6-Tris (glycidyloxymethyl) styrene can be mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth). Acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), represented by the formula (1). Examples of the compound to be used and the compound represented by the formula (2).

[In the formula, 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 together. When these are used in combination, the ratio of the compound represented by the formula (1) and the compound represented by the formula (2) (the compound represented by the formula (1): the compound represented by the formula (2)) is molar. By reference, it is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable.
As (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.

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

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. 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} ] Decane-8-yl (meth) acrylate (In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate" and sometimes "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate"), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) ) (Meta) acrylic acid ester such as acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;
Bicyclos such as bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene 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. Such as halogenated hydrocarbons; vinyl group-containing amides such as acrylamide and methacrylicamide; esters such as vinyl acetate; diene of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; and the like. ..

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

The resins [K1] to [K3] can be produced, for example, by polymerizing a monomer that derives a structural unit of a polymer in a solvent in the presence of a polymerization initiator. The solvent may be any one that dissolves each monomer, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later.

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

The resin (B) may be used alone or in combination of two or more, and may be 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth). ) Acrylic acid / vinyl toluene copolymer, benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate added, 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 the resin [K1] and / or the resin [K2] and the resins [K4] to the resins [K6] is preferable, and the resin [K1] and / or the resin [K2] and the resin [K4] are combined. ] Is more preferable.
When the resin [K1] and / or the resin [K2] and the resin [K4] to the resin [K6] are combined, the mass ratio thereof ({resin [K1] and / or the 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 polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 or more and 100,000 or less, more preferably 4,000 or more and 100,000 or less, and further preferably 5,000 or more and 80,000 or less. , Even more preferably 6,000 or more and 50,000 or less. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring 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 even 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, and more preferably. It is 180 mg-KOH / g or less, more preferably 150 mg-KOH / g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titrating with 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, based on the total amount of solids. It is preferably 23 to 55% by mass, and particularly preferably 25 to 55% by mass. When the content of the resin (B) is within the above range, the coloring pattern is easily formed, and the resolution and the residual film ratio of the coloring pattern 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. A compound having a structure is preferable. The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having five to six ethylenically unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. (A), (b) and (c) of. Polymerizable compounds having two ethylenically unsaturated bonds include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A bis (acryloyloxyethyl) ether and 3-methylpentanediol di. Examples include (meth) acrylate. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethyl propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and 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. Examples thereof include (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-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.

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 1 to 60% by mass, preferably 5 to 50% by mass, based on the total amount of solids. It is preferably 10 to 40% by mass, more preferably 12 to 35% by mass. The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65, on a mass basis. ~ 80:20. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring 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 that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat, 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 an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and 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-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Il] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1-one -2-Imine can be mentioned. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-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-cyclopentylpropane-1-one-2-imine is preferred, and N-benzoyloxy-1- (4-) Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

Alkylphenone compounds are 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one. And 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.

Alkylphenone compounds are 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1 It may be an oligomer of −hydroxycyclohexylphenylketone, 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 can be mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available 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, JP-A-6-. Examples thereof include compounds described in Japanese Patent Application Laid-Open No. 75373, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, Japanese Patent Application Laid-Open No. 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 and benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'. Benzoin compounds such as −methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, 2- Kinone compounds such as ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, titanosen compounds and the like. These are preferably used in combination with a polymerization initiator (particularly an amine-based polymerization initiator) described later.

The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass.

<Polymerization initiation aid>
The polymerization initiator is a compound or a sensitizer used to promote 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 initiator, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator include amine-based polymerization initiators, alkoxyanthracene-based polymerization initiators, thioxanthone-based polymerization initiators, and carboxylic acid-based polymerization initiators.

As amine-based polymerization initiators, alkanolamines such as triethanolamine, methyldiethanolamine, and 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, and among them, alkylaminobenzophenone such as 4,4'-bis (diethylamino) benzophenone; is preferable. Of these, alkylaminobenzophenone is preferable, and 4,4'-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene-based polymerization initiator include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, Included are 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

Examples of the carboxylic acid-based polymerization initiator include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid and N-phenylglycine.

When a polymerization initiator is used, its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the content of the polymerization initiation aid is within this range, a coloring 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, refer to 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 the formula (1), a _k represents the content of the solvent k with respect to the total solvent.
b _k represents the SP value of the solvent k based on the Fedors method.
n represents an integer of 1 or more. ]

When there is only one type of solvent (n = 1), the SP value of the solvent 1 becomes the S value as it is.
When there are two types of solvents (n = 2), the content a _{1 of the solvent 1 with respect to all the solvents and the content a 2} of the solvent 2 with respect to all the solvents are obtained with respect to the total amount of the solvent 1 and the solvent 2, respectively. , S value = (content rate of solvent 1 a ₁ × SP value of solvent 1) + (content rate of _{solvent 2 a 2} × SP value of solvent 2).
n is preferably 2 or more, more preferably an integer of 2 to 5, and even more 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 11. 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, still more preferably 10.80 (cal / cm 3). / 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. If the above range is not satisfied, the brightness tends to decrease, the dissolution time of the coloring composition layer becomes long, and the storage stability tends to deteriorate.

The solvent (E) is not limited, and solvents usually used in the art can be used alone or in combination of two or more. 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 (solvent containing OH in the molecule, -O −, −CO− and −COO− -free solvents), aromatic hydrocarbon solvents, amide solvents and dimethylsulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and pyruvate. Examples thereof include methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

Examples of the ether solvent 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, and propylene glycol monoethyl ether. , Propropylene 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 ether, diethylene glycol dibutyl ether, anisole, Examples include phenol and methyl anisole.

Examples of the ether ester solvent 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 Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, and propylene glycol diacetate.

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. Can be mentioned.

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

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

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

Two or more kinds of these solvents may be combined.

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 210 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and drying property. 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 preferable, and 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 and propylene glycol diacetate are more preferable.

The solvent (E) is one or more selected from the 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. It is preferable to contain one or more selected from the second solvent, and the solvent (E) is selected from one or more selected from the third solvent having a boiling point of less than 150 ° C. and the fourth solvent having a boiling point of 150 ° C. or higher. It is preferable to contain one or more kinds of solvents. 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 either 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 contained. Further, 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 above 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. A solvent belonging to any of the above 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, and is an ester solvent having an alkyl group, an ether solvent having an alkylene glycol, and a hydroxy group. More preferably, it is a ketone solvent having a boiling point of 155 ° C.: SP value of 11.93 (cal / cm ³ ) ^1/2 ) and propylene glycol diacetate (boiling point: 190 ° C.: SP value of 9.60 (cal)). / Cm ³ ) ^1/2 ) and 4-hydroxy-4-methyl-2-pentanone (boiling point 168 ° C.: SP value 11.70 (cal / cm ³ ) ^1/2 ) are more preferable.
Further, the solvent (ii) belonging to both the second solvent and the third solvent is preferably an ether solvent, more preferably an ether solvent having alkylene glycol, and propylene glycol monomethyl ether (boiling point: 120 ° C.: SP). A value of 11.27 (cal / cm ³ ) ^1/2 ) is even more preferred.

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, still more preferably 40% by mass or more, based on 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 even more preferably 95% by mass or less. If the first solvent does not satisfy the above range, the brightness of the obtained color filter tends to decrease, the dissolution time of the coloring composition layer becomes long, and the storage stability tends to deteriorate.

The content of the solvent (E) is usually 60 to 95% by mass, preferably 65 to 92% by mass, and more preferably 70 to 90% by mass with respect to the total amount of the colored curable resin composition. .. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..

<Leveling agent>
The colored curable resin composition may contain a leveling agent. Examples of the leveling agent include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant 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, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, Examples thereof include KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK).

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

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

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

<Other ingredients>
The color curable resin composition of the present invention is an additive known in the art, such as a filler, other polymer compounds, an adhesion accelerator, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. May include.

<Manufacturing method of colored curable resin composition>
The color curable resin composition of the present invention comprises, 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 initiator and other components.
It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Above all, the photolithography method is preferable. The photolithography method is a method in which a colored curable resin composition is applied to a substrate and 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 which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or 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, application, etc., and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

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

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.

First, a color curable resin composition is applied onto a substrate and dried by heat drying (prebaking) and / or vacuum drying to remove volatile components such as a solvent to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method and a slit and spin coating method.

The coloring composition layer is then exposed via a photomask to form the desired coloring pattern. An exposure device such as a mask aligner and a stepper should be used because it is possible to uniformly irradiate the entire exposed surface with parallel light rays and accurately align the photomask with the substrate on which the coloring composition layer is formed. Is preferable. A coloring pattern is formed on the substrate by developing the coloring composition layer after exposure in contact with a developing solution. By development, the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The developing method may be any of a paddle method, a dipping method and a 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 obtained coloring pattern. The color filter having the colored pattern and the colored coating film thus obtained may be further subjected to a 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 in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples,% and parts indicating the content or the amount used are based on mass unless otherwise specified.

Synthesis example 1
The following reaction was carried out in a nitrogen atmosphere. After putting 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 cooling tube and a stirrer, the mixed solution was ice-cooled. After adding 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) little by little over 30 minutes under ice-cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction solution, and the mixture was stirred at room temperature for 24 hours. After adding the reaction solution to 200 parts of ice water little by little, the mixture was allowed to stand at room temperature for 15 hours, and the water was removed by decantation to obtain a viscous solid 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 then purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C. to obtain 9.8 parts of the compound represented by the formula (CI-18).

The following reaction was carried out in a nitrogen atmosphere. 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 are put into a flask equipped with a cooling tube and a stirrer. Then, 12.2 parts of phosphorus oxychloride was added, and the mixture was stirred at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170 parts isopropanol. Then, the diluted reaction solution was poured into 300 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and when the mixture was allowed to stand for 30 minutes, it was separated into an organic layer and an aqueous layer. After discarding the aqueous layer by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and the mixture was stirred for 30 minutes and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with an evaporator to obtain a bluish-purple solid. Further, the blue-purple solid was dried under reduced pressure at 60 ° C. to obtain 18.4 parts of the compound represented by the formula (A-II-18).

The following reaction was carried out in a nitrogen atmosphere. After putting 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol into a flask equipped with a cooling tube and a stirrer, the mixture was stirred at room temperature for 30 minutes to prepare a blue solution. Then, 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.
53 parts of water was put into a beaker, and 11.8 parts of kegin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put 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 added dropwise to the previously prepared reaction solution over 1 hour. After further stirring at room temperature for 30 minutes, the mixture was filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol, dispersed for 1 hour, and then filtered, and the operation was repeated twice. The blue solid obtained by the operation was put into 200 parts of water, dispersed for 1 hour, and then filtered, and the operation was repeated twice. The blue solid obtained by the operation was dried under reduced pressure at 60 ° C. to obtain 17.1 parts of the 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 obtained solution was mixed at 110 ° C. Was stirred for 6 hours. The obtained reaction solution was cooled to room temperature, added to a mixture of 800 parts of water and 50 parts of 35 wt% hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue of suction filtration and then 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. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice-cooling, add 6.1 parts of a 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution, then add 19.4 parts of 35% hydrochloric acid little by little to dissolve and stir for 2 hours to add a diazonium salt. Suspension containing was obtained. Then, an aqueous solution prepared by dissolving 5.6 parts of amidosulfate (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added to inactivate excess sodium nitrite.
Then, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. did. The suspension containing the diazonium salt was added dropwise thereto over 15 minutes while appropriately adding a 10% sodium hydroxide solution so that the pH was in the range of 7 to 7.5. After completion of the dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. The mixture was stirred for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C. to obtain 11.7 parts (yield 87%) of the compound represented by the formula (p-2).

10 parts of the compound of the formula (p-2) was dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and ammonium 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 and refluxed for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline solution, and the red-orange solid obtained after filtration was dried at 60 ° C., and 13.6 parts of the compound represented by the formula (z-2) (z-2). The yield was 63%).

Synthesis example 4
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was placed therein, and the mixture was heated to 85 ° C. with stirring. Then 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution prepared by dissolving 225 parts of a mixture of decane-9-ylacrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyl toluene (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 the 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 of dropping the initiator solution, the mixture was kept at 85 ° C. for 4 hours and then cooled to room temperature to obtain a 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. Resin (B-1) weight-average molecular weight is 1.06 × 10 ^4, the acid value on solid basis is 115 mg-KOH / g, the molecular weight distribution was 2.01. The 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, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Then, nitrogen gas was introduced into the flask through the gas introduction pipe, and the atmosphere in the flask was replaced with nitrogen gas. After heating 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, and 51.7 g (0.6 mol) of methacrylate. , 90.0 g (0.9 mol) of methyl methacrylate, 5.2 g of azobisisobutyronitrile and 182 g of propylene glycol monomethyl ether acetate are added dropwise into the flask over 2 hours using a dropping funnel and dropped. After completion, the mixture was further stirred at 100 ° C. for 5 hours.
After the stirring was completed, air was introduced into the flask through the gas introduction tube to replace the atmosphere in the flask with air, and then 28.5 g of glycidyl methacrylate [0.2 mol (molar fraction with respect to the methacrylate used in this reaction). 33 mol%)], 1.3 g of trisdimethylaminomethylphenol and 0.165 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C. for 6 hours, with a solid content of 39.3% and a solid content acid value of 80 mgKOH. A / g resin (B-2) solution was obtained. The polystyrene-equivalent weight average molecular weight of the obtained resin (B-2) was 16,000.

Synthesis example 6
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 61.7 g (0.35 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 33.0 g (0.15 mol) of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton. ) And 136 g of propylene glycol monomethyl ether acetate to which 3.6 g of azobisisobutyronitrile was added was added dropwise to the flask over 2 hours from the dropping funnel, and the mixture was further stirred 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. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin (B-3) having a solid acid value of 79 mgKOH / g. The polystyrene-equivalent weight average molecular weight measured by GPC was 12,000, and the molecular weight distribution (Mw / Mn) was 2.1.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin polymer were measured by using the GPC method under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Sim-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Test solution concentration; 25 mg / mL (solvent; THF)
Flow velocity; 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the molecular weight distribution (Mw / Mn).

Examples 1 to 21 and Comparative Examples 1 and 2
Each component was mixed so as to have the compositions shown in Tables 4 to 5 to obtain a colored curable resin composition. The S values obtained from the formula (1) for the solvents used in Examples 1 to 21 and Comparative Examples 1 and 2 are 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) For} A1-1, mix the dispersant used as necessary, B-14 ⁾ , and the amount of propylene glycol monomethyl ether acetate described in column ^{E-15) and disperse in advance, or B} -14 ⁾ and the amount of propylene glycol monomethyl ether described in column E-5 ^{12) are mixed and dispersed in advance for use.
2)} The total resin B-1 content is shown.
³⁾ Shows the total content of propylene glycol monomethyl ether acetate.
⁶⁾ A1-2 is used by mixing an acrylic pigment dispersant, B-1 ¹⁰⁾ , and the amount of propylene glycol monomethyl ether acetate described in column E-1 ^{11) and dispersing them in advance.
7)} A1-3 is used by mixing an acrylic pigment dispersant, B-1 ¹⁰⁾ , and the amount of propylene glycol monomethyl ether acetate described in column E-1 ^{11) and dispersing them in advance.
8)} A1-4 is used by mixing the dispersant, B-14 ⁾ , and the amount of propylene glycol monomethyl ether acetate described in column ^{E-15) and dispersing them in advance.
9)} A1-5 is used by mixing the dispersant, B-14 ⁾ , and the amount of propylene glycol monomethyl ether acetate described in column ^{E-15) and dispersing them in advance.}

In Tables 4 to 5, each component represents the following. Further, the resin (B) showed a mass part in terms of solid content.
Colorant (A); 1-1; Compound colorant (A) represented by the formula (1-32); 1-2; Compound colorant (A) represented by the formula (z-2); A1- 1; Compound colorant (A) represented by the formula (AI-18); A1-2; C.I. 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); E-4); 4-Hydroxy-4-methyl-2-pentanone solvent (E); (E-5); Propylene glycol monomethyl ether surfactant (F); (F-1); Polyether-modified silicone oil (E-4); Torre Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.

<Making a colored pattern>
A color curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a color composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 80 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), 35 mJ / in an air atmosphere. The colored composition layer was irradiated with light at an exposure amount of ^{cm 2 (based on 365 nm).} As the photomask, a photomask having a 50 μm line-and-space pattern formed was used. The substrate on which the colored composition layer was formed after light irradiation was placed in a developing solution (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate by mass fraction) at 25 ° C. and 60. After dipping and developing for seconds and washing with water, post-baking was carried out at 230 ° C. for 30 minutes in an oven to obtain a colored pattern.

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

<Saturation evaluation>
The obtained coloring pattern is spectrophotometrically measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates in the XYZ color system of CIE using the characteristic function of the 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 Inc.) was washed successively with a neutral detergent, water and ethanol, and then dried. The colored curable resin composition was spin-coated on this glass substrate, and then prebaked at 100 ° C. for 3 minutes in a clean oven to form a colored composition layer.
Next, the substrate on which the coloring composition layer was formed was immersed in a developing solution having a liquid temperature of 25 ° C. (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate by mass fraction). The time when the portion 10 mm from the center of the substrate was completely melted was defined as the melting time. If the dissolution time is 25 seconds or less, the solubility is good. With such a color-curable resin composition, it can be said that productivity is high because a color pattern in which development defects such as residues are suppressed can be produced even if the development time is short. The results are shown in Tables 6-7.

<Storage stability>
The viscosity of the color-curable resin composition was measured using a viscometer (model; VISCMETER TV-30; manufactured by Toki Sangyo Co., Ltd .; rotation speed 100 rpm; measurement temperature 23 ° C.). After storing this color-curable composition 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.
Viscosity = (viscosity after storage for 7 days) / (viscosity immediately after preparation)

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

Claims (4)

It contains 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 represented by the formula (AI).
The solvent (E) is composed of n kinds of solvents k, and the S value obtained from the formula (1) is 8.75 (cal / cm ³ ) ^{1/2 or} more 10.33 (cal / cm ³ ) ^1/2. A colored curable resin composition characterized by the following.

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

[In the formula (AI), R ^{41 to} R ⁴⁴ each independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and a substituent having 6 to 20 carbon atoms which may have a substituent. It represents an aralkyl group having 7 to 30 carbon atoms which may have an aromatic hydrocarbon group or a substituent, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group , Substituent or unsubstituted, may be substituted with an 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 replaced with CO−. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom 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 independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, and an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group is an oxygen atom or -CO-. It may be replaced with. R ⁴⁸ and R ⁵² may be combined with 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 m-valent anion of a tungsten-containing heteropolyacid or isopolyacid.
m represents an arbitrary natural number.
When a plurality of cations represented by the following formulas are contained in one molecule, they may have the same structure or different structures.

[In the formula, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ are synonymous with the above, respectively. ]] One or more solvents (E) selected from the first solvent with SP value of less than ^{9.0 (cal / cm 3} ) ^{1/2 and SP value of 9.0 (cal / cm 3} ) ^1/2 or more. The colored curable resin composition according to claim 1, which comprises one or more selected from the second solvent. The color 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 higher. Sex resin composition. A method for producing a color filter , which comprises a step of forming a colored pattern or a colored coating film using the colored curable resin composition according to any one of claims 1 to 3.