JP6799943B2 - Color curable resin composition, color filter and display device - Google Patents

Description

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

A color filter formed from a color curable resin composition is used in a liquid crystal display device or the like or a solid-state image sensor. For example, in Patent Document 1, a compound represented by the following formula (1-8) and C.I. I. A colored curable resin composition containing Pigment Blue 15: 6 is described.

Japanese Unexamined Patent Publication No. 2013-50693

An object of the present invention is to provide a colored curable resin composition having good solvent resistance.

［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、又は炭素数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く、Ｒ⁴⁸とＲ⁵²とが互いに結合して、−ＮＨ−、−Ｏ−、−Ｓ−または−ＳＯ₂−を形成していてもよい。ただし、該アルキル基において、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。
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、酸素とを必須元素として含有する任意のｍ価のアニオンを表す。
ｍは任意の自然数を表す。］
［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。 The present invention includes the following inventions.
[1] A color-curable resin composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) is a dye skeleton. A colorant containing a compound (Aa) consisting of a cation having a cation, an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and a binder resin (B). However, a colored curable resin composition which is a binder resin containing the following resin (B1) and resin (B2).
(B1) Resin having a weight average molecular weight of 3,000 or more and less than 12,000 and an acid value in terms of solid content of 20 mg-KOH / g or more and 200 mg-KOH / g or less (B2) Weight average molecular weight of 12,000 The resin [2] resin (B1) having an acid value of 20 mg-KOH / g or more and 200 mg-KOH / g or less in terms of solid content of 100,000 or less is an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It is a copolymer containing a structural unit derived from at least one selected from the group consisting of, and a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The colored curable resin composition according to [1].
[3] The colored curable resin composition according to [1] or [2], wherein the compound (Aa) is a compound represented by the formula (AI).

[In the formula (AI), R ^{41 to} R ⁴⁴ each 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−. 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, or 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 substituted with −, and R ⁴⁸ and R ⁵² may be combined with each other to form −NH−, −O−, −S− or −SO ₂₋ . However, in the alkyl group, 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−.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.
[Y] ^m- represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.
m represents an arbitrary natural number. ]
[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].

The colored curable resin composition of the present invention has good solvent resistance.

In addition, in this specification, when a plurality of components are illustrated in parallel, it means that each element can be used alone or in combination of a plurality of types unless otherwise specified.

FIG. 1 is a schematic view showing a cross-sectional shape of a color filter.

The color curable resin composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D).

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, It may be referred to as compound (Aa)). The colorant (A) may further contain a dye (Ab).

Compound (Aa)
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 pigment skeleton, a xanthene pigment skeleton, an azine pigment skeleton, a cyanine pigment skeleton, an acridine pigment skeleton, an anthraquinone pigment skeleton, a squarylium pigment skeleton, and the like, which have an onium structure. Skeleton; Triarylmethane dye skeleton; Dye skeleton in which one or more of the aromatic hydrocarbon rings of the triarylmethane skeleton is an aromatic heterocycle and the like can be mentioned. Among them, a dye skeleton in which one or more of the aromatic hydrocarbon rings of the xanthene dye skeleton, the triarylmethane dye skeleton, and the triarylmethane dye skeleton is an aromatic heterocycle is more preferable, and more preferably the triarylmethane dye skeleton. It is a dye skeleton in which one or more of the aromatic hydrocarbon rings of the above is an aromatic heterocycle.

Examples of the anion derived from the compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen include a heteropolyacid anion containing tungsten and an isopolyacid anion containing tungsten. Preferably, phosphotungstate anion, silicate anion and tungsten-based isopolyacid anion are more preferable.

Examples of the tungsten-containing heteropolyacid anion and the tungsten-containing 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 silicate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ ] O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^{14 -} , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures thereof.

Examples of the compound (Aa) including a cation having a xanthene pigment skeleton and an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen include C.I. I. Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5, 169; C.I. I. Pigment Violet 1, 1: 1, 1: 2, 2, 2: 2; and the like.

Further, as the compound (Aa) composed of a cation having a triarylmethane dye skeleton and an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen, C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 18, 19, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 61, 62 and the like can be mentioned.

The compound (Aa) is preferably a compound represented by the formula (AI) (hereinafter, also referred to as a compound (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 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 substituent which the aromatic heterocycle of ring T ¹ may have includes a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which 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. 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 bond to form a ring with the nitrogen atom to which they bond.
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, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group. Linear alkyl groups such as groups; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and the like can be mentioned. 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 substituted or unsubstituted amino groups or halogen atoms. Examples of the substituted amino group include an alkylamino group such as a dimethylamino 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 preferably a perfluoroalkyl group 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 linear or branched chains 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 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.

Further, 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 and a terphenyl group, and preferably a phenyl group, a naphthyl group and a tolyl group. 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, Haloalkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; hydroxy group; sulfamoyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as 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 is 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, cation 1, cation 2 or cations 12 to 14 are particularly preferable, and cation 12 is most preferable. is there.

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

The content of the compound (Aa) in the color curable resin composition is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, based on the total amount of solids. It is more preferably 10% by mass or more and 60% by mass or less, and particularly preferably 15% by mass or more and 50% by mass or less. The content of the compound (Aa) is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 60% by mass or more, and particularly preferably 60% by mass or more, based on the total amount of the colorant (A). It is preferably 80% by mass or more and 100% 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 components excluding the solvent from the color curable resin composition of this invention. The total amount of solid content and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography and gas chromatography.

Compound (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.

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, the compound (a1-1) is particularly preferably a compound represented by the formula (a1-2).

［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Ｒ³³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 ^33s 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 (for example, methyl group, ethyl group, propyl group, isopropyl group) 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 and an ethyl group, and even more preferably a methyl group.
p and q are preferably integers of 0 to 2, preferably 1 or 2.

Among these, C.I. I. Sulfonamides of Acid Red 289, C.I. I. Quaternary Ammonium Salt of Acid Red 289, C.I. I. Sulfonamide of Acid Violet 102 or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred.

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.

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 .;
For example, C.I. I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46: 1, 82; C.I. I. Basic Orange 2, 24, 25; C.I. I. Basic Violet 18; C.I. I. Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; C.I. I. Basic Brown 1; C.I. I. Basic blue 41, 54, 64, 66, 67, 129 and the like can be mentioned.

As the azo dye, a metal complex salt azo dye is preferable. 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.
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 1-5.
D ⁺ represents hydron, or monovalent metal cation. ]

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.

The colorant (A) may further contain a pigment (Ac).
The pigment (Ac) is not particularly limited, and known pigments can be used. For example, pigments classified as pigments in the Color Index (The Society of Dyers and Colorists Publishing) (however, different from compound (Aa)) may be mentioned, and these may be used alone or in combination of two or more. be able to.
Specifically, 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, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. 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 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments; and C.I. I. Pigment Green 7, 36, 58 and other green pigments;

The pigment (Ac) can be a pigment dispersion liquid in which the pigment dispersant is uniformly dispersed in the solution by carrying out the dispersion treatment by containing the pigment dispersant. The pigments may be individually dispersed or a plurality of types may be mixed and dispersed.
Examples of the pigment dispersant include cation-based, anionic-based, nonionic-based, amphoteric, polyester-based, polyamine-based, and acrylic-based pigment dispersants. 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.), Solspers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), Ajinomoto Fine Examples thereof include Techno Co., Ltd. and Disperbyk (manufactured by Big Chemie).

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. By mixing the coloring mixed solution with the binder resin (B), the polymerizable compound (C), the polymerization initiator (D), and the like to prepare a coloring curable resin composition, the coloring curable resin composition can be obtained. The heat resistance of the formed 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, for example, 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.

When the colorant (A) contains the dye (Ab), the coloring mixture may contain a part or all, preferably a part of the dye (Ab) in advance. When the dye (Ab) is contained in the coloring mixture, the amount of the dye (Ab) is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the compound (Aa). , More preferably 1 to 5 parts by mass.

When the compound (Aa) is dispersed in a solvent to prepare a colored mixed solution, the colored mixed solution is prepared in advance with a part or all, preferably a part of the binder resin (B) contained in the coloring curable resin composition. It may be included. By including the binder resin (B) in advance, the dispersion stability of the colored curable resin composition can be further improved. The content of the binder 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.

The content of the colorant (A) in the color-curable resin composition is usually 1% by mass or more and 80% by mass or less, preferably 5% by mass or more and 70% by mass or less, based on the total amount of solids. , More preferably 10% by mass or more and 70% by mass or less, and particularly preferably 15% by mass or more and 65% by mass or less. When the content of the colorant (A) 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 components excluding the solvent from the color curable resin composition of this invention. The total amount of solid content and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography and gas chromatography.

When the colorant (A) contains a dye (Ab), the ratio (Aa / Ab) of the compound (Aa) to the dye (Ab) is preferably 1 or more, more preferably 2 or more, on a mass basis. It is more preferably 5 or more, particularly preferably 7 or more, preferably 600 or less, more preferably 300 or less, still more preferably 100 or less, still more preferably 50 or less, and particularly preferably 20 or less.
Further, when the colorant (A) contains a pigment (Ac), the ratio (Aa / Ac) of the compound (Aa) to the pigment (Ac) is preferably 0.1 or more, more preferably 0.5. As mentioned above, it is more preferably 0.7 or more, preferably 20 or less, more preferably 10 or less, still more preferably 8 or less.

When the colorant (A) contains the dye (Ab), the coloring mixed solution containing the dye (Ab) or the mixed solution containing the dye (Ab) and the solvent may be prepared in advance.

Binder resin (B)
The binder resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, It is preferably a polymer having a structural unit derived from (sometimes referred to as "(a)").
The binder resin (B) is a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”), and a structural unit. It is preferably a copolymer having other structural units.
As other structural units, the monomer (c) copolymerizable with the monomer (a) (however, it is different from the monomer (a) and the monomer (b). Hereinafter, “(c)”. A structural unit derived from (may be referred to as), a structural unit having an ethylenically unsaturated bond, and the like can be mentioned.

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) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the 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, Examples thereof include 4,6-tris (glycidyloxymethyl) styrene.

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, and 2-ethylhexyl (meth) acrylate. Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] 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;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) 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, etc. Unsaturated compound;
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 polymer having the structural unit derived from (a) can be produced, for example, by polymerizing a monomer leading to the structural unit of the 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 include the acid anhydrides mentioned in (a).

The resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the binder resin (B) is preferably 3,000 or more and 100,000 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 binder resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and even more preferably 1. It is 3 to 3.

The acid value (in terms of solid content) of the binder resin (B) is preferably 20 to 200 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the binder resin (B), and can be determined, for example, by titrating with an aqueous potassium hydroxide solution.

The binder resin (B) contains the following resin (B1) and resin (B2).
(B1) Resin having a weight average molecular weight of 3,000 or more and less than 12,000 and an acid value in terms of solid content of 20 mg-KOH / g or more and 200 mg-KOH / g or less (B2) Weight average molecular weight of 12,000 A resin having an acid value of 20 mg-KOH / g or more and 200 mg-KOH / g or less in terms of solid content and not more than 100,000.

By containing the resin (B1) and the resin (B2), the solvent resistance can be improved and the shape of the obtained pattern can be improved.

The weight average molecular weight of the resin (B1) is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 8,000 or more, and preferably 11,000 or less.

The acid value of the resin (B1) is preferably 50 mg-KOH / g or more, more preferably 80 mg-KOH / g or more, and preferably 180 mg-KOH / g or less in terms of solid content. More preferably, it is 150 mg-KOH / g or less.

Further, the resin (B1) has a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a cyclic ether structure having 2 to 4 carbon atoms. It is preferably a copolymer containing a structural unit derived from the monomer (b) having an ethylenically unsaturated bond. As the resin (B1), one kind or two or more kinds of copolymers can be used.

In the binder resin (B), the resin (B1) is preferably 60% by mass or more, more preferably 70% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less. Is.

The weight average molecular weight of the resin (B2) is preferably 70,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, and preferably 13,000 or more.

The acid value of the resin (B2) is preferably 50 mg-KOH / g or more, more preferably 80 mg-KOH / g or more, and preferably 180 mg-KOH / g or less in terms of solid content. More preferably, it is 150 mg-KOH / g or less.

The resin (B2) is preferably a polymer having a structural unit derived from at least one monomer (a) selected from the group consisting of at least unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. , A structural unit having a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and / or a monomer (c) copolymerizable with the monomer (a). It is preferably a copolymer having a structural unit derived from. As the resin (B2), one kind or two or more kinds of copolymers can be used.

The ratio (B1 / B2) of the contents of the resin (B1) and the resin (B2) is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and 15 or less on a mass basis. It is preferably, more preferably 10 or less, still more preferably 8 or less.

Further, the weight average molecular weight of the polymer derived from the resin (B2) (weight average molecular weight 12,000 or more and 100,000 or less) and the polymer derived from the resin (B1) (weight average molecular weight 3,000 or more 12, The ratio (B2 / B1) to the weight average molecular weight (less than 000) is preferably 1.2 or more, more preferably 2 or more, preferably 4 or less, and more preferably 3 or less. ..

When preparing the colored mixed solution, the colored mixed solution may contain a resin (B1) and a resin (B2), and preferably contains the resin (B1). Further, when preparing the colored mixed solution, both the resins (B1) and (B2) are contained in the remaining binder resin (B) excluding the binder resin (B) derived from the colored mixed solution. Is preferable.

The total amount of the resin (B1) and the resin (B2) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 95% by mass or more in the binder resin (B). Is 99% by mass or more.

The total content of the binder resin (B) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably 13 to 60% by mass, particularly, based on the total amount of solids. It is preferably 17 to 55% by mass. When the content of the binder 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. 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. The polymerizable compound (C) is preferably a compound having a (meth) acrylic acid ester structure.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. (A), (b) and (c) of. The polymerizable compound having two ethylenically unsaturated bonds includes 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, and more preferably 12 to 37% by mass. The content ratio of the binder resin (B) to the polymerizable compound (C) (binder resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35, based on mass. : 65-80: 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 and the like by the action of light and 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), N-1919, and NCI-930 (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'. Benzophenone 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 ethyl anthraquinone 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 polymerization initiator (D) is at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound (more preferably, an alkylphenone compound). It is preferable to combine with.
In the polymerization initiator (D), the O-acyloxime compound is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 100% by mass or less.

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

Polymerization Initiator A polymerization initiator is a compound or 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 preferred, and 4,4'-bis (diethylamino) benzophenone is preferred. 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, Examples include 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 the polymerization initiation aid is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 1 part with respect to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). It is 20 parts by mass. 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)
The colored curable resin composition may contain a solvent (E). 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, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), 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.

Ester solvents 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 monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-3. Examples thereof include methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether and anisole.

Examples of the ether ester solvent include butyl methoxyacetate, methyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-. Ethyl 2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene Examples thereof include glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate 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 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, cyclohexanone, 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, cyclohexanone, ethyl 3-ethoxypropionate, N, N-dimethylformamide and N-methylpyrrolidone are more preferred.

The content of the solvent (E) is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 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 silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, 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, TSF4446, 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 Corporation), 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. .3 mass% or less.

Other Ingredients The color curable resin composition of the present invention is known in the art as a filler, other polymer compounds, adhesion accelerators, antioxidants, light stabilizers, chain transfer agents and the like, if necessary. Additives may be included.

Method for Producing Color Curable Resin Composition The color curable resin composition of the present invention is, for example, a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent ( It can be prepared by mixing E) and, if necessary, a leveling agent, a polymerization initiator and other components. In addition to the colorant (Aa), a colorant such as a pigment can be further mixed. It is preferable that the pigment is mixed with a part or all of the solvent (E) in advance and used in the state of a pigment dispersion liquid dispersed by using a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. .. At this time, if necessary, a part or all of the pigment dispersant and the binder resin (B) may be blended.
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.

Method for Producing 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. Of these, 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, etc. 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 heating and drying (prebaking) and / or under reduced pressure 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. Since 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, use an exposure device such as a mask aligner and a stepper. 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 color curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

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. In a flask equipped with a cooling tube and a stirrer, 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 charged. 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 of 2-propanol. 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 the mixture was allowed to stand for 30 minutes to separate 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 bluish 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. 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol were put into a flask equipped with a cooling tube and a stirrer, and then 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, stirred 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, stirred 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. The mixture was stirred for 6 hours. The obtained reaction solution was cooled to room temperature, added to a mixed solution 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, 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 amide sulfate (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 put into 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and 12 parts of ammonium sulfate (III) and water (manufactured by Wako Pure Chemical Industries, Ltd.) 3 After adding 1 part and 1.1 part of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated under reflux for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of a 20% saline solution, and the red-orange solid obtained after filtration was dried at 60 ° C. to 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 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace it with a nitrogen atmosphere, 371 parts by weight of 1-methoxy-2-propyl acetate was added, and the mixture was heated to 85 ° C. with stirring. .. Then, 54 parts by weight of acrylic acid, 225 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 and / and 9-ylacrylate, vinyltoluene (isomer mixture). A mixed solution of 81 parts and 80 parts by weight of 1-methoxy-2-propyl acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by weight of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts by weight of 1-methoxy-2-propyl acetate was added dropwise over 5 hours. After completion of dropping the initiator solution, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to have a B-type viscosity (23 ° C.) of 246 mPas, a solid content of 37.5% by weight, and a solution acid value of 43 mg-KOH / g. Polymer B1 was obtained. The weight average molecular weight Mw of the produced copolymer was 10600 and the dispersity was 2.01.

Synthesis example 5
An appropriate amount of nitrogen was poured into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace it with a nitrogen atmosphere, 141 parts by weight of ethyllactate and 178 parts by weight of propylene glycol monomethyl ether acetate were placed, and heated to 85 ° C. with stirring. did. Then, 38 parts by weight of acrylic acid, 25 parts by weight of a mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] deca-8 and / and 9-ylacrylate, 137 parts by weight of cyclohexylmaleimide, 2 A mixed solution of 50 parts by weight of -hydroxyethyl methacrylate and 338 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 5 parts by weight of 2,2-azobisisobutyronitrile in 88 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the copolymer was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer B2 having a B-type viscosity (23 ° C.) of 23 mPas, a solid content of 25.6% by weight, and a solution acid value of 28 mg-KOH / g. Obtained. The weight average molecular weight Mw of the produced copolymer was 8000 and the dispersity was 2.1.

Synthesis example 6
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 300 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 85 ° C. with stirring. Then 54 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] Dissolve 306 parts of a mixture of decane-9-ylacrylate (content ratio 50:50 in molar ratio) and 24 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 316 parts of diethylene glycol ethyl methyl ether. The resulting solution was added dropwise into the flask over 5 hours. After completion of the dropping, the mixture was kept at 85 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin B3) solution. The solid content of the resin B3 solution was 37.0%, and the viscosity measured with a B-type viscometer (23 ° C.) was 88 mPas. The weight average molecular weight of the resin B3 is 7.5 × 10 ^3, acid value on solid basis is 91mg-KOH / g, the molecular weight distribution was 1.93. Resin B3 has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer were measured by using the GPC method under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-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 degree of dispersion (Mw / Mn).

Examples 1 to 5 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.

In Tables 4 to 5, each component represents the following. Further, the binder 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; Salt 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; Pigment Blue 1
Colorant (A); A1-5; Pigment Red 81
Dispersant: (BYK (registered trademark) -LPN6919 (manufactured by Big Chemie Japan))
Binder resin (B); (B-1); resin (B-1)
Binder resin (B); (B-2); Resin (B-2)
Binder resin (B); (B-3); resin (B-3)
Binder resin (B); (B-4); Copolymer of methacrylic acid and benzyl methacrylate [The ratio (molar ratio) of methacrylic acid unit to benzyl methacrylate unit is 35:65, and the acid value is 135 mg-KOH / g. , Polystyrene-equivalent weight average molecular weight is 25,000] (However, at the time of mixing, a propylene glycol monomethyl ether acetate solution having a solid content of 34% was used.)
Polymerizable compound (C); (C-1); dipentaerythritol hexaacrylate (KA)
YARAD (registered trademark) 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); Propylene Glycol Monomethyl Ether Solvent (E); (E-3); Diacetone Alcohol Surfactant (F) ); (F-1); polyether-modified silicone oil (Tore 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 an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to create 35 mJ / in an air atmosphere. The colored composition layer was light-irradiated with 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 colored composition layer after light irradiation is immersed and developed in a developing solution (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalene sulfonate by mass fraction) at 25 ° C. for 60 seconds. After washing with water, post-baking was performed 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 Table 6.

<Saturation evaluation>
The obtained coloring pattern was spectrophotometrically measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates in the CIE XYZ color system were used using the characteristic function of the C light source. (X, y) and brightness Y were measured. The results are shown in Table 6.

<Preparation of colored coating film>
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 light-irradiated with 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. A colored coating was obtained by post-baking at 230 ° C. for 30 minutes in an oven.

<Solvent resistance evaluation>
The chromaticity of the obtained colored coating film was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). Then, the obtained colored coating film was immersed in a large excess amount of N-methyl-2-pyrrolidone maintained at 23 ° C. for 30 minutes, and the chromaticity of the colored coating film after immersion was measured in the same manner.
The color difference ΔEab * of the colored coating films of Examples 1 to 5 was 3 or less, almost no change in hue was observed, and good characteristics as a color filter were exhibited. The results are shown in Table 6.

<Colored pattern shape evaluation>
The shape of the obtained coloring pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). The shape shown in (p1) of FIG. 1 (so-called forward taper shape) was marked with ◯, and the shape shown in (p2) was marked with Δ. With the shape shown in (p1), cracks and peeling tend to be less likely to occur when the inorganic film is laminated on the colored pattern. The results are shown in Table 6.

The colored curable resin composition of the present invention has good solvent resistance.

Claims (5)

A color curable resin composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D).
Coloring agent (A) containing 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. Is an agent
Binder resin (B), Ri binder resin der containing the resin (B2) below the resin (B1),
The resin (B2) and the resin ratio of the weight average molecular weight of (B1) (B2 / B1) is 25,000 / 10,600 to 3 der Ru colored curable resin composition.
(B1) Resin having a weight average molecular weight of 3,000 or more and less than 12,000 and an acid value in terms of solid content of 20 mg-KOH / g or more and 200 mg-KOH / g or less (B2) Weight average molecular weight of 12,000 A resin having an acid value of 20 mg-KOH / g or more and 200 mg-KOH / g or less in terms of solid content and not more than 100,000. A structural unit from which the resin (B1) is derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
The colored curable resin composition according to claim 1, which is a copolymer containing a cyclic ether structure having 2 to 4 carbon atoms and a structural unit derived from a monomer having an ethylenically unsaturated bond. The colored curable resin composition according to claim 1 or 2, wherein the compound (Aa) is a compound represented by the formula (AI).

[In the formula (AI), R ^{41 to} R ⁴⁴ each 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, or 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 substituted with −, and R ⁴⁸ and R ⁵² may be combined with each other to form −NH−, −O−, −S− or −SO ₂₋ . However, in the alkyl group, 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−.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.
[Y] ^m- represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements.
m represents an arbitrary natural number. ] A color filter formed from the colored curable resin composition according to any one of claims 1 to 3. A display device including the color filter according to claim 4.

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