JP2015096598A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition which is used for forming a color filter, that is incorporated in a liquid crystal display device, a solid-state image pickup element or the like, and which contains a dye having high heat resistance.SOLUTION: A dye compound comprises: a dye cation shown by formula (A-VI) (in which R-Rare each H, a halogen atom, an alkyl group or the like, independently;R-Rare each H, a substituted/unsubstituted alkyl group, independently;it does not matter if Rand Rand/or Rand Rare bonded to one another to form a ring together with a nitrogen atom;A is a substituted/unsubstituted aromatic group or a substituted/unsubstituted heteroaromatic group); and an anion having boron or aluminum and two or more reactive groups in one molecule thereof. The colored curable resin composition contains the dye compound.

Description

  The present invention relates to a compound and a colored curable resin composition.

As a colored curable resin composition for forming a color filter included in a liquid crystal display device or the like, a solid-state imaging device or the like, Patent Document 1 discloses a compound represented by the formula (A-III-1), a binder resin, and a solvent. , A colored curable resin composition containing a polymerization initiator and a curing agent is described.

WO2012 / 128318

  Conventionally known colored curable resin compositions containing the above-mentioned compounds have not been sufficiently satisfactory in terms of heat resistance.

［式（Ａ−ＶＩ）中、Ｒ^１Ａ〜Ｒ^８Ａ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、または炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）を表す。
Ｒ^９Ａ〜Ｒ^１２Ａは、それぞれ独立して、水素原子、アミノ基もしくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）、または置換されていてもよいアリール基を表す。Ｒ^９ＡとＲ^１０Ａ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、Ｒ^１１AとＲ^１２A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。
Ａは、置換基を有していてもよい芳香族基、または置換基を有していてもよいヘテロ芳香族基を表す。］
［４］染料カチオンが式（Ａ−ＶＩ）で表されるカチオンであり、２個以上の反応性基を有するアニオンが式（４）で表されるアニオンである［３］に記載の染料化合物。

［式（Ａ−ＶＩ）中、Ｒ^１Ａ〜Ｒ^８Ａ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、または炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）を表す。
Ｒ^９Ａ〜Ｒ^１２Ａは、それぞれ独立して、水素原子、アミノ基もしくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）、または置換されていてもよいアリール基を表す。Ｒ^９ＡとＲ^１０Ａ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、Ｒ^１１AとＲ^１２A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。
Ａは、置換基を有していてもよい芳香族基、または置換基を有していてもよいヘテロ芳香族基を表す。］

［式（４）中、Ｗ^１およびＷ^２は、それぞれ独立に、反応性基とプロトン供与性基とを有する化合物のプロトン供与性基からプロトンが放出されることにより形成される基を表す。
Ｍは、ホウ素又はアルミニウムを表す。］
［５］［１］〜［４］のいずれかに記載の化合物を含む着色剤。
［６］アントラキノン染料およびテトラアザポルフィリン染料からなる群から選ばれる少なくとも１つの染料をさらに含む［５］に記載の着色剤。
［７］顔料をさらに含む［５］または［６］に記載の着色剤。
［８］［５］〜［７］のいずれかに記載の着色剤（Ａ）と、樹脂（Ｂ）と、重合性化合物（Ｃ）と、重合性開始剤（Ｄ）と、溶剤（Ｅ）とを含む着色性硬化性樹脂組成物。
［９］さらに、無色の金属錯体（Ｆ）を含む［８］に記載の着色硬化性樹脂組成物。
［１０］［９］または［９］に記載の着色硬化性樹脂組成物から形成される塗膜。
［１１］［８］または［９］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。
［１２］［１１］に記載のカラーフィルタを含む表示装置。 The present invention provides the following [1] to [12].
[1] A dye compound comprising a dye cation and an anion having two or more reactive groups.
[2] The dye compound according to [1], wherein the anion having two or more reactive groups is a boron-containing anion or an aluminum-containing anion.
[3] The dye compound according to [1] or [2], wherein the dye cation is a cation represented by the formula (A-VI).

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 20 carbon atoms (the carbon constituting the alkyl group). An oxygen atom may be inserted between the atoms).
R ^{9A to} R ^12A are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom is inserted between carbon atoms constituting the alkyl group) Or an aryl group which may be substituted. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent, or a heteroaromatic group which may have a substituent. ]
[4] The dye compound according to [3], wherein the dye cation is a cation represented by formula (A-VI), and the anion having two or more reactive groups is an anion represented by formula (4) .

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 20 carbon atoms (the carbon constituting the alkyl group). An oxygen atom may be inserted between the atoms).
R ^{9A to} R ^12A are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom is inserted between carbon atoms constituting the alkyl group) Or an aryl group which may be substituted. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent, or a heteroaromatic group which may have a substituent. ]

[In Formula (4), W ¹ and W ² each independently represent a group formed by releasing a proton from a proton donating group of a compound having a reactive group and a proton donating group.
M represents boron or aluminum. ]
[5] A colorant comprising the compound according to any one of [1] to [4].
[6] The colorant according to [5], further comprising at least one dye selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye.
[7] The colorant according to [5] or [6], further including a pigment.
[8] The colorant (A) according to any one of [5] to [7], the resin (B), the polymerizable compound (C), the polymerizable initiator (D), and the solvent (E). A colorable curable resin composition comprising:
[9] The colored curable resin composition according to [8], further comprising a colorless metal complex (F).
[10] A coating film formed from the colored curable resin composition according to [9] or [9].
[11] A color filter formed from the colored curable resin composition according to [8] or [9].
[12] A display device including the color filter according to [11].

  The colored curable resin composition containing the compound of the present invention can form a color filter having excellent heat resistance.

２個以上の反応性基を有するアニオンとしては、含ホウ素アニオンまたは含アルミニウムアニオンが好ましい。 The dye compound of the present invention comprises a dye cation and an anion having two or more reactive groups. Examples of the dye cation include cations in known dyes having chloride ions as anions. Specifically, examples of the dye cation include cyanine dyes shown below.

The anion having two or more reactive groups is preferably a boron-containing anion or an aluminum-containing anion.

  As the dye compound of the present invention, a compound comprising a cation represented by the formula (A-VI) and an anion represented by the formula (4) is preferable.

［式（Ａ−ＶＩ）中、Ｒ^１Ａ〜Ｒ^８Ａ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、または炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）を表す。
Ｒ^９Ａ〜Ｒ^１２Ａは、それぞれ独立して、水素原子、アミノ基もしくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）、または置換されていてもよいアリール基を表す。Ｒ^９ＡとＲ^１０Ａ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、Ｒ^１１AとＲ^１２A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。
Ａは、置換基を有していてもよい芳香族基または置換基を有していてもよいヘテロ芳香族基を表す。］ The cation represented by the formula (A-VI) includes tautomers thereof.

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 20 carbon atoms (the carbon constituting the alkyl group). An oxygen atom may be inserted between the atoms).
R ^{9A to} R ^12A are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom is inserted between carbon atoms constituting the alkyl group) Or an aryl group which may be substituted. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent or a heteroaromatic group which may have a substituent. ]

［式（Ａ−Ｉ）中、Ｘは、酸素原子または硫黄原子を示す。
Ｒ^４１〜Ｒ^４６は、それぞれ独立して、水素原子、アミノ基もしくはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）、または置換されていてもよいアリール基を表す。
Ｒ^４１とＲ^４２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、Ｒ^４３とＲ^４４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、Ｒ^４５とＲ^４６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。
Ｒ^４７〜Ｒ^５４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、または炭素数１〜８のアルキル基（該アルキル基を構成する炭素原子間に酸素原子が挿入されていてもよい）を表す。
Ｒ^５５は、水素原子、炭素数１〜２０のアルキル基、または置換されていてもよいアリール基を表す。］ The cation represented by the formula (A-VI) is preferably a cation represented by the formula (AI). The cation represented by the formula (AI) includes tautomers thereof.

[In the formula (AI), X represents an oxygen atom or a sulfur atom.
R ^{41 to} R ⁴⁶ are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom is inserted between carbon atoms constituting the alkyl group) Or an aryl group which may be substituted.
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 ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms (an oxygen atom is inserted between carbon atoms constituting the alkyl group). May be).
^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted. ]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{1A to} R ^12A in formula (A-VI) and R ^{41 to} R ⁴⁶ and R ⁵⁵ in formula (AI) include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclopropyl group, Examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like, for example, a group represented by the following formula. In the following formula, * represents a bond with a carbon atom or a nitrogen atom. Especially, a C1-C8 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and a C1-C4 alkyl group is further more preferable.

In the alkyl group having 1 to 20 carbon atoms represented by R ^{1A to} R ^12A in formula (A-VI) and R ^{41 to} R ⁴⁶ in formula (AI), oxygen is bonded between carbon atoms constituting the alkyl group. Examples of the group into which an atom is inserted include a group represented by the following formula. In the following formula, * represents a bond with a carbon atom or a nitrogen atom. Among these, in the alkyl group having 1 to 10 carbon atoms, a group in which an oxygen atom is inserted between carbon atoms constituting the alkyl group is preferable, and in the alkyl group having 1 to 6 carbon atoms, the alkyl group is constituted. A group in which an oxygen atom is inserted between carbon atoms is more preferable.

Examples of the alkyl group having 1 to 20 carbon atoms substituted with an amino group or a halogen atom represented by R ^{9A to} R ^12A in formula (A-VI) and R ^{41 to} R ⁴⁶ in formula (AI) include: And groups represented by the following formulas. Examples of the amino group include an amino group which may be substituted with one or two alkyl groups having 1 to 8 carbon atoms such as an amino group, a dimethylamino group, a diethylamino group, and a methylethylamino group. In the following formula, * represents a bond with a nitrogen atom.

In the optionally substituted aryl group represented by R ^{9A to} R ^12A in formula (A-VI) and R ^{41 to} R ⁴⁶ and R ⁵⁵ in formula (AI), the substituent may be a fluorine atom, Halogen atoms such as chlorine atom and iodine; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group; chloromethyl A haloalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxy group; a sulfamoyl group; An alkylsulfonyl group etc. are mentioned.
Specific examples of the aryl group which may be substituted include groups represented by the following formulas. In the following formula, * represents a bond with a nitrogen atom.

In the formula (A-VI), R ^9A and R ^10A , R ^11A and R ^12A are combined and the ring formed with the nitrogen atom to which they are bonded includes pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring and the like. Can be mentioned.

In the formula (A-I), R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are bonded to form a nitrogen atom together with the pyrrolidine ring, morpholine ring, piperidine. A ring, a piperazine ring, and the like.

In the formula (A-VI), R ^{1A to} R ^8A are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, each independently. And more preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

R ^{9A to} R ^12A in formula (A-VI) and R ^{41 to} R ⁴⁶ and R ⁵⁵ in formula (AI) are each independently an alkyl group having 1 to 20 carbon atoms from the viewpoint of ease of synthesis. Or it is preferable that it is the aryl group which may be substituted, and it is more preferable that it is a C1-C8 alkyl group or the aryl group represented by a following formula each independently. In the following formula, * represents a bond with a nitrogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ in formula (AI) (an oxygen atom may be inserted between carbon atoms constituting the alkyl group) include: Examples include groups represented by the following formula. In the following formula, * represents a bond with a carbon atom.

In the formula (AI), R ^{47 to} R ⁵⁴ are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, each independently. And more preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

Ａで表される置換基を有していてもよい芳香族基としては、例えば、下記式で表される基が挙げられる。＊は、炭素原子との結合手を表す。 Examples of the aromatic group which may have a substituent represented by A in the formula (A-VI) include C6-C14 aromatic groups such as a phenyl group and a naphthyl group.
Examples of the substituent that the aromatic group may have include an optionally substituted amino group, an alkoxy group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, a hydroxy group, and —SO ₃ ^—. It is done.
As the amino group which may be substituted, an amino group which may be substituted with one or two alkyl groups having 1 to 8 carbon atoms such as amino group, dimethylamino group, diethylamino group and methylethylamino group; Examples thereof include a phenylamino group, a methoxyphenylamino group, an ethoxyphenylamino group, a 1-methylphenylamino group, and groups described below.

Examples of the aromatic group that may have a substituent represented by A include groups represented by the following formulae. * Represents a bond with a carbon atom.

  Of these, a group represented by the formula (A1-2) and a group represented by the formula (A1-6) are preferable.

Ａで表される置換基を有していてもよいヘテロ芳香族基としては、例えば、下記式で表される基が挙げられる。＊は、炭素原子との結合手を表す。 The heteroaromatic group which may have a substituent represented by A in Formula (A-VI) represents an aromatic group having at least one heteroatom as a ring component. Examples of the hetero atom in the heteroaromatic group include a nitrogen atom, a sulfur atom, and an oxygen atom.
The heteroaromatic group is preferably a C3-C10 heteroaromatic group having at least one nitrogen atom, and examples thereof include an imidazolyl group, a thiazolyl group, and an oxazolyl group.
Examples of the substituent that the heteroaromatic group may have include an optionally substituted amino group, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxy group,- SO _3- ^{and the} like can be mentioned.
As the amino group which may be substituted, an amino group which may be substituted with one or two alkyl groups having 1 to 8 carbon atoms such as amino group, dimethylamino group, diethylamino group and methylethylamino group; Examples thereof include a phenylamino group, a methoxyphenylamino group, an ethoxyphenylamino group, a 1-methylphenylamino group, and groups described below.

Examples of the heteroaromatic group optionally having a substituent represented by A include groups represented by the following formulae. * Represents a bond with a carbon atom.

  Of these, a group represented by the formula (A1-12) and a group represented by the formula (A1-13) are preferable.

  In the formula (AI), X represents an oxygen atom or a sulfur atom. From the viewpoint of ease of synthesis, a sulfur atom is preferred.

  Specific examples of the cationic dye represented by the formula (A-VI) include dyes of the following formula.

式（Ａ−Ｉ）で表されるカチオンとしては、下記表１に示すカチオン１〜カチオン１２等の染料が挙げられる。表１において、カチオン１は、式（Ａ−Ｉ−ａ）で示されるカチを表す。

Examples of the cation represented by the formula (AI) include dyes such as cation 1 to cation 12 shown in Table 1 below. In Table 1, the cation 1 represents a kats represented by the formula (AIa).

  Especially, as a cation represented by a formula (AI), the cation 1-cation 6, the cation 11, or the cation 12 is preferable, and the cation 1, the cation 2, or the cation 12 is especially preferable.

As an anion having two or more reactive groups, a boron-containing anion or an aluminum-containing anion is preferable, and an anion represented by the following formula (4) is more preferable.
The boron-containing anion means an anion containing a boron atom, and the aluminum-containing anion means an anion containing an aluminum atom.

［ 式（４）中、Ｗ^１及びＷ^２は、それぞれ独立に、反応性基とプロトン供与性基とを有する化合物のプロトン供与性基からプロトンが放出されることにより形成される基を表す。
Ｍは、ホウ素原子又はアルミニウム原子を表す。］

[In Formula (4), W ¹ and W ² each independently represent a group formed by releasing a proton from a proton donating group of a compound having a reactive group and a proton donating group.
M represents a boron atom or an aluminum atom. ]

Examples of the reactive group include a group having an ethylenically unsaturated bond. Specific examples include groups represented by the following. * Represents a binding hand.

W ¹ and W ² each independently have one or more reactive groups. When the number of reactive groups is 2 or more, the brightness tends to be excellent.

Examples of the compound having a reactive group and a proton donating group include compounds represented by the following.

［式中、Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４は、それぞれ独立して、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又は反応性基を表す。ただし、Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４のうち少なくとも１つは、反応性基である。
Ｍは、ホウ素原子又はアルミニウム原子を表す。］ Examples of the anion represented by the formula (4) include anions (BC-1) to anions (BC-43) shown in Tables 2 and 3 (M represents a boron atom or an aluminum atom). .

[Wherein R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a reactive group. Represent. However, at least one of R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ is a reactive group.
M represents a boron atom or an aluminum atom. ]

中でも、式（４）で表されるアニオンとしては、アニオン（ＢＣ−４）〜アニオン（ＢＣ−６）、アニオン（ＢＣ−１３）〜アニオン（ＢＣ−１５）、アニオン（ＢＣ−２２）〜アニオン（ＢＣ−２４）、アニオン（ＢＣ−２９）、アニオン（ＢＣ−３２）、アニオン（ＢＣ−３９）が好ましい。

Especially, as an anion represented by Formula (4), anion (BC-4)-anion (BC-6), anion (BC-13)-anion (BC-15), anion (BC-22)-anion (BC-24), anion (BC-29), anion (BC-32), and anion (BC-39) are preferred.

A dye compound formed from a dye cation and an anion having two or more reactive groups (hereinafter sometimes referred to as a dye (A1)) is a dye cation and an anion having two or more reactive groups. It can manufacture by mixing an alkali metal salt in a solvent.
For example, the description is given by a dye cation formed from a dye cation represented by the formula (AI) and an anion represented by the formula (4) (hereinafter sometimes referred to as a dye (A1-1)). Then, the compound represented by formula (A-II) (hereinafter sometimes referred to as compound (A-II)) and the alkali metal salt of the anion represented by formula (4) are mixed in a solvent. Can be manufactured. Examples of the alkali metal include lithium, sodium and potassium.

Solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform. Is mentioned.
Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable. When these solvents are used, the solubility of the alkali metal salt of the anion represented by the compound (A-II) and the formula (4) tends to be high.
When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.
Mixing with the compound (A-II) and the alkali metal salt of the anion represented by the formula (4) may be carried out by dissolving both in the above solvent or not.

  The mixing temperature of the compound (A-II) and the alkali metal salt of the anion represented by the formula (4) is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, and further preferably 20 ° C to 100 ° C. ° C. The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, and further preferably 3 hours to 12 hours.

When a solvent compatible with water is used, the solution is mixed, and further stirred for 1 to 3 hours as necessary, and then the precipitate is obtained by filtration to obtain the dye (A1-1). Can be obtained. If necessary, the obtained dye (A1-1) may be washed with ion-exchanged water.
When a solvent that is not compatible with water is used, the reaction mixture and ion-exchanged water are mixed and further stirred for 1 to 3 hours as necessary, and then the organic layer is obtained by liquid separation to obtain a dye ( A solution containing A1-1) can be obtained. If necessary, the solution may be washed with ion exchange water. The dye (A1-1) can be obtained by removing the solvent from the solution containing the dye (A1-1).

Compound (A-II) includes, for example, a compound represented by formula (BI) (hereinafter sometimes referred to as compound (B-1)) and a compound represented by formula (C-I) ( Hereinafter, it may be referred to as a compound (C-1).). Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

式（Ｂ−Ｉ）及び式（Ｃ−Ｉ）中、Ｒ^４１〜Ｒ^５５は、それぞれ前記と同じ意味を表す。

In formula (BI) and formula (CI), R ^{41 to} R ⁵⁵ each represent the same meaning as described above.

Compound (A-II) includes a compound represented by formula (B-II) (hereinafter sometimes referred to as compound (B-II)) and a compound represented by formula (C-II) (hereinafter, Compound (C-II) in some cases) can be reacted. Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

式（Ｂ−ＩＩ）及び式（Ｃ−ＩＩ）中、Ｒ^４１、Ｒ^４２、Ｒ^４５〜Ｒ^５０及びＲ^５５は、それぞれ上記と同じ意味を表す。

In formula (B-II) and formula (C-II), R ⁴¹ , R ⁴² , R ^{45 to} R ⁵⁰ and R ⁵⁵ each represent the same meaning as described above.

With respect to the compound represented by the formula (BI), the amount of the compound represented by the formula (CI) is preferably used with respect to 1 mol of the compound represented by the formula (BI). Is 0.5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less.
With respect to the compound represented by the formula (B-II), the amount of the compound represented by the formula (C-II) is preferably used with respect to 1 mol of the compound represented by the formula (B-II). Is 0.5 mol or more and 8 mol or less, more preferably 1 mol or more and 3 mol or less.

The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

  Any reaction is preferably carried out in an organic solvent from the viewpoint of yield. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl Ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (BI) or the compound represented by the formula (B-II). More preferably, it is 2 parts by mass or more and 10 parts by mass or less.

  The above reaction is preferably carried out in the presence of a condensing agent from the viewpoint of yield. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride and the like.

  The amount of the condensing agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (BI) or the compound represented by the formula (B-II). Yes, more preferably 0.2 parts by mass or more and 5 parts by mass or less.

  The method for obtaining the target compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with alcohol (for example, methanol etc.), and the precipitated crystals can be collected by filtration. The reaction mixture is preferably added to the alcohol. The temperature at which the reaction mixture is added is preferably −100 ° C. or higher and 50 ° C. or lower, more preferably −80 ° C. or higher and 0 ° C. or lower. Thereafter, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  Examples of the method for producing the compounds (BI) and (B-II) include various known methods, for example, the methods described in West German Patent Application P3928243.0.

  As a manufacturing method of compound (CI) and (C-II), a well-known various method, for example, the method described in patent document 1, is mentioned.

  As the alkali metal salt of the anion represented by the formula (4), commercially available ones may be used. For example, Patent No. 4097704, Patent No. 4341251 and Journal of The Electrochemical Society, Vol. 148, Phase 1, 2001. Can be produced by the method described in 1. above.

Specific examples of the dye compound formed from the cation represented by formula (A-VI) and the anion represented by formula (4) include, for example, any one selected from cation 1 to cation 12 shown in Table 1 And the compounds formed by any anions selected from the anions (BC-1) to (BC43) shells shown in Tables 2 and 3 and the compounds represented by the following formulas.

  The colored curable resin composition of the present invention comprises a colorant (A) containing a dye compound (dye (A1)) comprising a dye cation and an anion having two or more reactive groups, a resin (B), And a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

<Colorant (A)>
The colorant (A) contains the dye (A1), and further contains at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye (hereinafter sometimes referred to as a dye (A2)). May be included.

As the anthraquinone dye, a known substance may be used. As an anthraquinone dye, for example,
C. I. Solvent Yellow 117 (hereinafter, CI Solvent Yellow is omitted, and only the number is described), 163, 167, 189,
C. I. Solvent orange 77, 86,
C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Red 80,
C. I. Acid Green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse Yellow 51,
C. I. Disperse violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modern Red 3, 11,
C. I. Modern Blue 8
Etc. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye.

  More preferable anthraquinone dyes include compounds represented by formula (3-1) to formula (3-11).

  As an anthraquinone dye, the compound represented by Formula (3-4) and the compound represented by Formula (3-11) are more preferable. When these anthraquinone dyes are used, a high-contrast coating film or pattern can be formed, and there is little generation of foreign matter, and a coating film or pattern with excellent light resistance can be formed.

The tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule. Further, when the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.
Specific examples of the tetraazaporphyrin dye include a compound represented by the formula (2-1) to a compound represented by the formula (2-38).

As the tetraazaporphyrin dye, a compound represented by the formula (2-29) is preferable.
A composition containing this tetraazaporphyrin dye can form a high-contrast coating film or pattern, and generates less foreign matter.

  The content of the dye (A1) is preferably 0.5% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A).

  The content of the dye (A2) is preferably 1 to 100 parts by mass and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the dye (A1).

  In addition to the dyes (A1) and (A2), the colorant (A) further contains other dyes, pigments (P), or a mixture thereof for toning, that is, to adjust spectral characteristics. You may go out.

  Examples of other dyes include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamides of acid dyes, and the like. For example, Color Index (The Society of Examples include compounds classified as dyes by Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing). According to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferably used.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. C. such as Disperse Yellow 54, 76 I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, blue dyes, violet dyes and red dyes are preferred.
These dyes may be used alone or in combination of two or more.

The pigment (P) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
Examples of the pigment include 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, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  The pigment (P) is preferably at least one selected from the group consisting of phthalocyanine pigments and dioxazine pigments, and more preferably C.I. I. At least one selected from the group consisting of CI Pigment Blue 15: 6 and CI Pigment Violet 23. By including the pigment, it is easy to optimize the transmission spectrum, and the heat resistance, light resistance and chemical resistance of the color filter are improved.

  The content of the colorant (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 5% by mass with respect to the total amount of the solid content. % To 50% by mass. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

  In this specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as “resin (B)”) is derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A copolymer containing structural units.
Examples of such a resin (B) include the following resins [K1] to [K6].
Resin [K1] at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and having 2 to 4 carbon atoms A copolymer of a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3] Copolymer of (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

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

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

  Examples of (b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a tetrahydrofuryl group and an ethylenically unsaturated bond. And monomers.

  (B) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. .

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 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
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, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene are preferred.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3- menu Resin such as ru-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) Acrylic acid copolymer, resin such as benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin with glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, resin with glycidyl (meth) acrylate added, tricyclodecyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate Resin [K4] such as a resin to which a relate is added; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / Resin such as a resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) Examples thereof include a resin [K6] such as a resin obtained by reacting acrylic acid with a resin further reacted with tetrahydrophthalic anhydride.

  For example, the resin [K1] can be obtained by, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.

The resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability.
Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution and remaining film ratio of the colored 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 the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

  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. And the above-mentioned (a), (b) and (c).

  Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there.
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

  Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane. -1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, Irgacure (registered trademark) 369,907 379 (above, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) pro Down-1-one oligomer, alpha, alpha-diethoxyacetophenone, and benzyl dimethyl ketal.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913).

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

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

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

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
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, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di Propylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Chill acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N- methylpyrrolidone is more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.
When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

［ 式（１０）中、Ｒ^8１〜Ｒ^8４は、それぞれ独立に、水素原子、炭素数1〜4のアルキル基又はヒドロキシ基を表す。］ <Colorless metal complex (F)>
The colored curable resin composition of the present invention may contain a colorless metal complex (F).
Examples of the colorless metal complex (F) include a zinc complex represented by the formula (10).

Wherein (10), R ⁸¹ ~R ⁸⁴ independently represents a hydrogen atom, an alkyl group or a hydroxy group having 1 to 4 carbon atoms. ]

Examples of the alkyl group having 1 to 4 carbon atoms in R ^{81 to} R ⁸⁴ in the formula (10) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert group. -A butyl group is mentioned. Specific examples of the zinc complex represented by the formula (10) include those shown in Table 4. Of these, (10) -18 is preferred from the viewpoint of heat resistance.

  The content of the colorless metal complex is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less with respect to the colorant (A).

<Other ingredients>
The colored curable resin composition of the present invention comprises, if necessary, a polymerization initiation aid, a leveling agent (H), an antioxidant, a filler, other polymer compounds, an adhesion promoter, a light stabilizer, a chain transfer. An additive known in the art, such as an agent, may be included.
Examples of the leveling agent (H) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and a colorless used as necessary. It can be prepared by mixing the metal complex (F), the leveling agent (H), the polymerization initiation assistant (D1), the antioxidant (J), and other components.
The pigment in the case of containing the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
It is preferable to prepare a solution by dissolving the colorant (A) dye in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  By using the colored curable resin composition of the present invention, a color filter having particularly high brightness can be produced. The color filter 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

Synthesis example 1
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 32.2 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 49.9 parts of a compound represented by the formula (BI-7). Yield 51%

Synthesis example 2
The following reaction was performed in a nitrogen atmosphere. 9. In a flask equipped with a condenser and a stirrer, 9.9 parts of the compound represented by the formula (BI-7), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.2 parts of a compound represented by the formula (A-II-7). Yield 85%

Identification of compound represented by formula (A-II-7) (mass spectrometry) ionization mode = ESI +: m / z = 619.3 [M-Cl] ⁺
Exact Mass: 654.3

Synthesis example 3
10 parts of methyl 5-allyl-3-methoxysalicylate (manufactured by Tokyo Chemical Industry Co., Ltd.) is added to 200 parts of water and 100 parts of methanol, then 1.8 parts of sodium hydroxide is added, and heated at 50 ° C. for 2 hours. did. After cooling, the reaction solution was added to 200 parts of ice water and stirred for 1 hour, and then hydrochloric acid was added until pH became 2. The resulting precipitate was filtered and washed with 200 parts of ion-exchanged water to obtain 8.5 parts of a compound represented by the following formula (BC-14-A).

Synthesis example 4
8.5 parts of the compound represented by the formula (BC-14-A) was added to 20 parts of methanol, then 0.8 part of sodium hydroxide was added, and the mixture was stirred at 30 degrees for 1 hour. Next, 1.2 parts of boron was added, and the mixture was further stirred at room temperature for 1 hour. Then, it stirs at 80 degreeC for 2 hours, The precipitate which arises after cooling is filtered, It wash | cleans with 200 parts of ion-exchange water, The obtained white solid is dried at 60 degreeC for 24 hours, The following formula (BC-14-Na 6.8 g of an anion represented by

Example 1
The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of a compound represented by the formula (A-II-7), 6.7 parts of a compound represented by the formula (BC-14-Na), and N, After adding 100.0 parts of N-dimethylformamide, the mixture was stirred at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 12.0 parts of a compound represented by the formula (AI-7). Yield 83%

Synthesis Example 6
An appropriate amount of nitrogen was allowed to flow into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) (trade name “E-DCPA”, manufactured by Daicel Corporation) 171 parts propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was dropped over about 5 hours using a dropping pump. On the other hand, a solution prepared by dissolving 26 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in a flask over about 5 hours using another dropping pump. It was dripped. After dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1) solution having a solid content of 43.5%. The obtained resin (B-1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Synthesis example 7
250.4 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while purging with nitrogen, and heated to 120 ° C. Next, 37.4 parts of methacrylic acid, 61.3 parts of benzyl methacrylate, 18.5 parts of glycidyl methacrylate, and 19.2 parts of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 6.13 parts of t-butyl hydroperoxide (Nippon Yushi Co., Ltd. perbutyl O) was added to the monomer mixture consisting of This was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 120 ° C. for 2 hours for aging. Next, the inside of the flask was replaced with air, and 0.96 parts of trisdimethylaminomethylphenol (DMP-30) and hydroquinone 0. 145 parts were charged into the aged product and the reaction was continued at 120 ° C. for 6 hours to obtain a copolymer (resin (B-2) solution having a solid content of 38.4% by mass and an acid value of 122 mg-KOH / g. The obtained resin (B-2) had a weight average molecular weight Mw of 10700 and a molecular weight distribution of 2.18, and the weight average molecular weight and the molecular weight distribution were the same as those of the resin (B-1). It was measured by.

(Preparation of colored curable resin composition)
Example 2
Colorant (A): 20 parts of a dye represented by the formula (AI-7);
Colorant (A): 6 parts of a dye represented by formula (3-11);
Alkali-soluble resin (B): 53 parts of resin (B-2) (solid content conversion);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4.1 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 380 parts of 4-hydroxy-4-methyl-2-pentanone;
Leveling agent (H): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.12 parts;
Antioxidant: 0.2 part of Sumilizer GP and 6.1 part of zinc complex (F) :( 10) -18 were mixed to obtain a colored curable resin composition.

Comparative Example 1
Colorant (A): 26 parts of a dye represented by the formula (A-III-1);
Alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (H): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

[Production of color filters]
The obtained colored curable resin composition was applied by spin coating on a 2 inch square glass substrate (# 1737; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. . After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), exposure was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.8 μm).

[Heat resistance evaluation]
The coating film of the colored photosensitive resin composition was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result of performing the above heat resistance evaluation on the coating film obtained in Example 2, the color difference (ΔEab *) was 6.2. Moreover, as a result of carrying out heat resistance evaluation similarly about the comparative example 1, color difference ((DELTA) Eab *) was 12.1 and it turned out that this-application compound is excellent in heat resistance.

  When the colored curable resin composition containing the compound of the present invention is used, a color filter having excellent heat resistance can be provided. The color filter 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.

Claims (12)

  A dye compound comprising a dye cation and an anion having two or more reactive groups.   The dye compound according to claim 1, wherein the anion having two or more reactive groups is a boron-containing anion or an aluminum-containing anion. The dye compound according to claim 1 or 2, wherein the dye cation is a cation represented by the formula (A-VI).

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 20 carbon atoms (the carbon constituting the alkyl group). An oxygen atom may be inserted between the atoms).
R ^{9A to} R ^12A are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom is inserted between carbon atoms constituting the alkyl group) Or an aryl group which may be substituted. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent, or a heteroaromatic group which may have a substituent. ] The dye compound according to claim 3, wherein the dye cation is a cation represented by formula (A-VI), and the anion having two or more reactive groups is an anion represented by formula (4).

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 20 carbon atoms (the carbon constituting the alkyl group). An oxygen atom may be inserted between the atoms).
R ^{9A to} R ^12A are each independently an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom, an amino group or a halogen atom (an oxygen atom is inserted between carbon atoms constituting the alkyl group) Or an aryl group which may be substituted. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent, or a heteroaromatic group which may have a substituent. ]

[In Formula (4), W ¹ and W ² each independently represent a group formed by releasing a proton from a proton donating group of a compound having a reactive group and a proton donating group.
M represents a boron atom or an aluminum atom. ]   The coloring agent containing the compound in any one of Claims 1-4.   The colorant according to claim 5, further comprising at least one dye selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye.   The colorant according to claim 5 or 6, further comprising a pigment.   The colorant (A) according to any one of claims 5 to 7, a resin (B), a polymerizable compound (C), a polymerizable initiator (D), and a solvent (E). Colorable curable resin composition.   Furthermore, the colored curable resin composition of Claim 8 containing a colorless metal complex (F).   The coating film formed from the colored curable resin composition of Claim 8 or 9.   A color filter formed from the colored curable resin composition according to claim 8.   A display device comprising the color filter according to claim 11.