JP2020183509A - Compound and coloring composition - Google Patents

Abstract

To provide a compound and a coloring composition having an excellent absorbance retention before and after a light resistance test.SOLUTION: The present invention provides a compound represented by formula (I). [In formula (I), Q is a group represented by formula (Q1): *-CR6=CR5-NR3-**, formula (Q2): *-O-CR5=N-**, formula (Q3): *-S-CR5=N-**, formula (Q4): *-N=CR5-NR3-**, or formula (Q5): *-NR6-CR5=N-** (* is a bond to a carbon atom to which R4 bonds). R1-R5 each denote a hydrogen atom or a C1-6 monovalent hydrocarbon group, and -CH2- contained in the hydrocarbon group is optionally substituted with -O- or -CO-. R6 is a monovalent aromatic group, or a C1-6 monovalent aliphatic hydrocarbon group, and -CH2- contained in the aliphatic hydrocarbon group is optionally substituted with -O- or -CO-].SELECTED DRAWING: None

Description

The present invention relates to novel compounds and coloring compositions.

Various dyes are known as colorants contained in a colored resin composition that forms a color filter contained in a liquid crystal display device, a solid-state image sensor, or the like. Patent Document 1 discloses a filter for a plasma display panel using a squarylium dye.

Japanese Unexamined Patent Publication No. 2001-183522

The present invention relates to a compound having an excellent absorbance retention rate before and after a light resistance test, a coloring composition containing the compound, a coloring curable resin composition containing the coloring composition, a color filter formed from these compositions, and the like. An object of the present invention is to provide a display device including a color filter.

［式（Ｉ）中、
Ｑは、
式（Ｑ１）：＊−ＣＲ^６＝ＣＲ^５−ＮＲ^３−＊＊、
式（Ｑ２）：＊−Ｏ−ＣＲ^５＝Ｎ−＊＊、
式（Ｑ３）：＊−Ｓ−ＣＲ^５＝Ｎ−＊＊、
式（Ｑ４）：＊−Ｎ＝ＣＲ^５−ＮＲ^３−＊＊、又は
式（Ｑ５）：＊−ＮＲ^６−ＣＲ^５＝Ｎ−＊＊
で表される基を表す（＊は、Ｒ^４が結合する炭素原子との結合手を表す。）。
Ｒ^１〜Ｒ^５は、それぞれ独立して、水素原子又は置換基を有していてもよい炭素数１〜６の１価の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｒ^６は、置換基を有していてもよい１価の芳香族基、又は、置換基を有していてもよい炭素数１〜６の１価の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。］
なお、＊＊は、Ｑの他方の結合手を表す。
〔２〕 前記〔１〕に記載の化合物を含む着色剤と樹脂とを含む着色組成物。
〔３〕 前記〔２〕に記載の着色組成物と、重合性化合物と、重合開始剤とを含む着色硬化性樹脂組成物。
〔４〕 前記〔２〕に記載の着色組成物、又は、前記〔３〕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〕 前記〔４〕に記載のカラーフィルタを含む表示装置。 The present invention provides the following compounds, coloring compositions, coloring curable resin compositions, color filters, and display devices.
[1] A compound represented by the formula (I).

[In formula (I),
Q is
Equation (Q1): * -CR ⁶ = CR ^5- NR ³ -**,
Equation (Q2): * -O-CR ⁵ = N-**,
Equation (Q3): * -S-CR ⁵ = N-**,
Equation (Q4): * -N = CR ^5- NR ³ -**, or Equation (Q5): * -NR ⁶ -CR ⁵ = N-**
Represents a group represented by (* represents a bond with a carbon atom to which R ⁴ is bonded).
R ^{1 to} R ⁵ each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent, and are contained in the hydrocarbon group −CH ₂ −. May be replaced with -O- or -CO-.
R ⁶ represents a monovalent aromatic group which may have a substituent or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and the fat. -CH _2- contained in the group hydrocarbon group may be replaced with -O- or -CO-. ]
Note that ** represents the other bond of Q.
[2] A coloring composition containing a colorant containing the compound according to the above [1] and a resin.
[3] A coloring curable resin composition containing the coloring composition according to the above [2], a polymerizable compound, and a polymerization initiator.
[4] A color filter formed from the coloring composition according to the above [2] or the coloring curable resin composition according to the above [3].
[5] A display device including the color filter according to the above [4].

The coloring composition containing the compound of the present invention has an excellent absorbance retention before and after the light resistance test.

(A) and (b) are schematic cross-sectional views showing an example of an optical filter. (A) is a schematic cross-sectional view showing an example of an organic EL display device using an optical filter, and (b) is a schematic cross-sectional view showing an example of a liquid crystal display device using an optical filter.

［式（Ｉ）中、全ての符号は、上記と同じ意味を表す。］ (Compound represented by formula (I))
The present invention relates to a compound represented by the following formula (I) (hereinafter, may be referred to as “compound (I)”).

[In formula (I), all symbols have the same meanings as above. ]

In compound (I), when Q is a group represented by the formula (Q1), compound (I) represents the following structure.

In compound (I), when Q is a group represented by the formula (Q2), compound (I) represents the following structure.

In compound (I), when Q is a group represented by the formula (Q3), compound (I) represents the following structure.

In compound (I), when Q is a group represented by the formula (Q4), compound (I) represents the following structure.

In compound (I), when Q is a group represented by the formula (Q5), compound (I) represents the following structure.

Compound (I) has an excellent absorbance retention rate before and after the light resistance test, for example, when it is used in a coloring composition described later. Compound (I) is also excellent in heat resistance when it is used as a coloring composition, for example.

In compound (I) when Q is a group represented by the formula (Q1), in addition to the notation represented by the above structure, there are tautomers having a resonance structure as represented by the following formula, for example. To do.

In compound (I) when Q is a group represented by the formula (Q2), in addition to the notation represented by the above structure, there are tautomers having a resonance structure as represented by the following formula, for example. To do.

In compound (I) when Q is a group represented by the formula (Q3), in addition to the notation represented by the above structure, for example, a tautomer having a resonance structure represented by the following formula exists. To do.

In compound (I) when Q is a group represented by the formula (Q4), in addition to the notation represented by the above structure, for example, a tautomer having a resonance structure represented by the following formula exists. To do.

In compound (I) when Q is a group represented by the formula (Q5), in addition to the notation represented by the above structure, for example, a tautomer having a resonance structure represented by the following formula exists. To do.

Compound (I) includes any tautomer, including the tautomers exemplified above.

The hydrocarbon group in the formula (I) is a group composed of a carbon atom and a hydrogen atom, and the carbon number of the hydrocarbon group includes the carbon number of the substituent.
The carbon number of the group in which -CH ₂ − contained in the hydrocarbon group is replaced with -O- or -CO- refers to the number of carbon atoms before being replaced by -O- or -CO-.

In the formula (I), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms in R ^{1 to} R ⁵ include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon group.

The monovalent aliphatic hydrocarbon group in R ^{1 to} R ⁵ may be a monovalent aliphatic saturated hydrocarbon group or a monovalent aliphatic unsaturated hydrocarbon group. The monovalent aliphatic hydrocarbon group may be a linear or branched chain hydrocarbon group, or may be an alicyclic hydrocarbon group.
The monovalent aliphatic saturated hydrocarbon group in R ^{1 to} R ⁵ includes a linear alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group; isopropyl. Branched alkyl groups having 3 to 6 carbon atoms such as groups, isobutyl groups, sec-butyl groups, tert-butyl groups, isopentyl groups and neopentyl groups; 3 to 6 carbon atoms such as cyclopropyl groups, cyclopentyl groups and cyclohexyl groups. Examples thereof include an alicyclic saturated hydrocarbon group.
Examples of the monovalent aliphatic unsaturated hydrocarbon group in R ^{1 to} R ⁵ include a linear alkenyl group having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group; sec- A branched alkenyl group having 4 to 6 carbon atoms such as a butenyl group and an isobutenyl group; a linear alkynyl group having 3 to 6 carbon atoms such as a propynyl group, an n-butynyl group, an n-pentynyl group, and an n-hexynyl group; Branched alkynyl group having 4 to 6 carbon atoms such as sec-butynyl group and isobutynyl group; cycloalkenyl group having 3 to 6 carbon atoms such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group; cyclobutylenyl group, Examples thereof include a cycloalkynyl group having 4 to 6 carbon atoms such as a cyclopentynyl group and a cyclohexynyl group.

When the monovalent aliphatic hydrocarbon group in R ^{1 to} R ⁵ contains a cyclic structure, the number of carbon atoms constituting the cyclic structure is preferably 3 to 6, and more preferably 5 or 6.

Examples of the monovalent aromatic hydrocarbon group in R ^{1 to} R ⁵ include a phenyl group.

In the formula (I), examples of the substituent that the hydrocarbon group in R ^{1 to} R ⁵ may have include a halogen atom, a hydroxy group, an amino group, a nitro group, a sulfamoyl group, a sulfo group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
A halogen atom is preferable as the substituent that the hydrocarbon groups in R ^{1 to} R ⁵ may have.

In formula (I), −CH ₂₋ contained in a monovalent hydrocarbon group having 1 to 6 carbon atoms may be replaced with −O− or −CO−. Examples of such groups include -C (= O) CH ₃ and -C (= O) -OCH ₂ CH ₃ .

In the formula (I), R ¹ and R ² are preferably hydrogen atoms or alkyl groups independently of each other, and more preferably both are hydrogen atoms.
It is preferable that R ^{3 to} R ⁵ are independently hydrogen atoms or alkyl groups. It is more preferable that R ³ is a hydrogen atom, and it is more preferable that R ⁴ and R ⁵ are independently alkyl groups.

Wherein (I), a monovalent aromatic group in R ⁶ can be a monovalent aromatic hydrocarbon group, or a monovalent aromatic heterocyclic group. The monovalent aromatic group may have a monocyclic structure or a condensed ring structure.
The number of carbon atoms of the monovalent aromatic hydrocarbon group is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 13.
The monovalent aromatic hydrocarbon group includes phenyl group, methylphenyl group, dimethylphenyl group, mesityl group, propylphenyl group, butylphenyl group, hexylphenyl group, 2-ethylhexylphenyl group, naphthyl group, biphenyl group and tar. Aryl groups having 6 to 16 carbon atoms such as phenyl group, propylbiphenyl group, anthracenyl group, phenanthryl group, pyrenyl group and fluorenyl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group and phenylbutyl group can be mentioned. ..
The monovalent aromatic hydrocarbon group contains a group in which the hydrogen bonded to the carbon constituting the aromatic ring of the aromatic hydrocarbon group is substituted with an alkyl group or an aryl group, and the substituted alkyl group is used. The included −CH ₂₋ may be replaced with −O− or −CO−.
Preferably the number of carbon atoms constituting the aromatic ring contained in the monovalent aromatic hydrocarbon group for R ⁶ is 6 to 18, and more preferably 6-12.

The number of carbon atoms of the monovalent aromatic heterocyclic group is usually 2 to 30, preferably 4 to 20, and more preferably 4 to 10.
The heteroatom in the monovalent aromatic heterocyclic group represents a nitrogen atom, an oxygen atom, a sulfur atom and the like. The number of complex atoms contained in the monovalent aromatic heterocyclic group is preferably 1 to 3, and more preferably 1.
The monovalent aromatic heterocyclic groups include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, isothiazole, imidazole, pyrazole, frazane, triazole, oxazole, isooxazole, tetrazole, pyran, pyridine, thiopyran, Pyridazine, pyrimidine, pyrazine, triazine, benzofuran, isobenzofuran, benzothiophene, indol, isoindole, indrine, indolin, isoindolin, chromene, isochromen, chroman, isochroman, benzopyran, quinoline, isoquinoline, quinolidine, benzoimidazole, benzothiazole , Benzothiazol, indazole, naphthylidine, quinoxalin, quinazoline, quinazolidine, cinnoline, phthalazine, purine, pteridine, carbazole, xanthene, phenanthridin, aclysine, β-carbolin, perimidine, phenanthrolin, thiantolen, phenoxatiin, phenoxazine , Phenazine and other heterocyclic compounds from which one hydrogen atom has been removed.
The monovalent aromatic heterocyclic group includes a group in which the hydrogen contained in the above-mentioned group is substituted with a hydrocarbon group such as an alkyl group or an aryl.
Preferably the number of carbon atoms constituting the aromatic heterocyclic ring contained in the monovalent aromatic heterocyclic group in R ⁶ is 6 to 18, and more preferably 6-12.

In formula (I), the aromatic substituent which group may have, in R ^6, a halogen atom, hydroxy group, an amino group, a nitro group, an aryloxy group, an aryl group, an aryloxycarbonyl group, carboxy Examples thereof include a group, a carbamoyl group, a sulfamoyl group, a sulfo group and the like.

Wherein (I), a monovalent aliphatic hydrocarbon group for R ⁶ may be a monovalent aliphatic saturated hydrocarbon group may be a monovalent aliphatic unsaturated hydrocarbon group. The monovalent aliphatic hydrocarbon group may be a linear or branched chain hydrocarbon group, or may be an alicyclic hydrocarbon group.
The number of carbon atoms of the monovalent aliphatic hydrocarbon group in R ⁶ is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10, and further preferably 1 to 6. preferable. When the monovalent aliphatic hydrocarbon group contains a cyclic structure, the number of carbon atoms constituting the cyclic structure is preferably 3 to 6, and more preferably 5 or 6.

The monovalent aliphatic hydrocarbon group in R ⁶ may be a monovalent aliphatic saturated hydrocarbon group or a monovalent aliphatic unsaturated hydrocarbon group. The monovalent aliphatic hydrocarbon group may be a linear or branched chain hydrocarbon group, or may be an alicyclic hydrocarbon group.
The monovalent aliphatic saturated hydrocarbon group for R ^6, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, 1 to 4 carbon atoms, such as nonyl and decyl groups, Linear alkyl groups of ~ 16; branched alkyl groups having 3 to 16 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; cyclo Cycloalkyl group having 3 to 16 carbon atoms such as propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclopentenyl group; alkylcycloalkyl group having 4 to 16 carbon atoms such as propylcyclohexyl group and octylcyclohexyl group; cyclohexyl Examples thereof include a cycloalkylalkyl group having 4 to 16 carbon atoms such as a butyl group and a cyclohexyloctyl group.
The monovalent aliphatic unsaturated hydrocarbon group in R ^6, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl and 2 to 16 carbon atoms such as decenyl, Linear alkenyl group; branched alkenyl group such as sec-butenyl group and isobutenyl group; propynyl group, n-butynyl group, n-pentynyl group, n-hexynyl group, n-heptinyl group, n-octynyl group, n Linear alkynyl groups having 4 to 16 carbon atoms such as −noninyl group and n-decynyl group; branched alkynyl groups having 4 to 16 carbon atoms such as sec-butynyl group and isobutynyl group; cyclopropenyl group, cyclobutenyl group, Cycloalkenyl groups having 3 to 16 carbon atoms such as cyclopentenyl group and cyclohexenyl group; alkenylcycloalkyl groups having 5 to 16 carbon atoms such as propenylcyclohexyl group and 1-decenylcyclohexyl group; cyclobutynyl group, cyclopentynyl Examples thereof include a cycloalkynyl group having 4 to 16 carbon atoms such as a group and a cyclohexynyl group.
The monovalent aliphatic unsaturated hydrocarbon group in R ^6, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl and 2 to 16 carbon atoms such as decenyl, Linear alkenyl group; branched alkenyl group such as sec-butenyl group and isobutenyl group; propynyl group, n-butynyl group, n-pentynyl group, n-hexynyl group, n-heptinyl group, n-octynyl group, n Linear alkynyl groups having 4 to 16 carbon atoms such as −noninyl group and n-decynyl group; branched alkynyl groups having 4 to 16 carbon atoms such as sec-butynyl group and isobutynyl group; cyclopropenyl group, cyclobutenyl group, Cycloalkenyl groups having 3 to 16 carbon atoms such as cyclopentenyl group and cyclohexenyl group; alkenylcycloalkyl groups having 5 to 16 carbon atoms such as propenylcyclohexyl group and 1-decenylcyclohexyl group; cyclobutynyl group, cyclopentynyl Examples thereof include a cycloalkynyl group having 4 to 16 carbon atoms such as a group and a cyclohexynyl group.

When the monovalent aliphatic hydrocarbon group of R ⁶ contains a cyclic structure, the number of carbon atoms constituting the cyclic structure is preferably 3 to 8, and more preferably 4 to 6.

In the formula (I), examples of the substituent that the aliphatic hydrocarbon group in R ⁶ may have include the substituents exemplified in R ^{1 to} R ⁵ .
As the substituent that the hydrocarbon group in R ⁶ may have, a halogen atom is preferable.

-CH _2- contained in the aliphatic hydrocarbon group in R ⁶ may be replaced with -O- or -CO-. Examples of such groups include -C (= O) CH ₃ and -C (= O) -OCH ₂ CH ₃ .

Examples of the compound (I) include a compound represented by the following formula.

［式（ＩＶ−１）及び式（ＩＶ−３）中、Ｒ^７及びＲ^８は、それぞれ独立して、炭素数１〜２０のアルコキシ基を表す。
式（ＩＶ−２）、式（ＩＶ−３）、及び式（ＩＶ−４）中、Ｒ^３〜Ｒ^６は、上記と同じ意味を表す。
式（ＩＶ−５）中、Ｒ^１及びＲ^２は、上記と同じ意味を表す。］ (Method for producing compound (I) (1))
First, the compound (I) of the present invention has a compound represented by the following formula (IV-1) (hereinafter, may be referred to as “compound (IV-1)”) and the following formula (IV-2). A compound represented by the following formula (IV-3) (hereinafter, "Compound (IV-3)") is reacted with a represented compound (hereinafter, may be referred to as "Compound (IV-2)"). From this compound (IV-3), a compound represented by the following formula (IV-4) (hereinafter, may be referred to as “compound (IV-4)”) is obtained. Next, this compound (IV-4) is reacted with a compound represented by the following formula (IV-5) (hereinafter, may be referred to as “compound (IV-5)”) to cause compound (I). Can be manufactured.

Wherein (IV-1) and formula (IV-3), ^{R 7} and ^{R 8} each independently represents an alkoxy group having 1 to 20 carbon atoms.
In the formula (IV-2), the formula (IV-3), and the formula (IV-4), R ^{3 to} R ⁶ have the same meanings as described above.
In formula (IV-5), R ¹ and R ² have the same meanings as above. ]

Wherein (IV-1) and formula (IV-3), examples of the alkoxy group having 1 to 20 carbon atoms in ^{R 7} and ^{R 8,} a methoxy group, an ethoxy group, n- propoxy group, iso- propoxy group, n- Butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-cyclohexyloxy group, n-dodecyloxy group And so on.

Examples of the compound (IV-1) include a compound represented by the following formula.

Examples of the compound (IV-2) include a compound represented by the following formula.

Examples of the compound (IV-3) include a compound represented by the following formula.

Examples of the compound (IV-4) include a compound represented by the following formula.

Examples of the compound (IV-5) include a compound represented by the following formula.

In the step of producing the compound (IV-3), it is preferable to react the compound (IV-1) and the compound (IV-2) in an organic solvent.
Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; hydrocarbon solvents such as hexane, cyclohexane and decalin, and ether solvents such as tetrahydrofuran, 1,4-dioxane and dimethoxyethane; chlorobenzene, dichlorobenzene, chloroform and the like. Halogenized hydrocarbon solvent; alcohol solvent such as methanol, ethanol, isopropanol, butanol; nitro hydrocarbon solvent such as nitrobenzene; ketone solvent such as methyl isobutyl ketone; N, N-dimethylformamide, 1-methyl-2-pyrrolidone and the like. Examples thereof include the amide solvent of the above, and these may be mixed and used. Of these, butanol is preferred. The amount of the organic solvent used is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less with respect to 1 part by mass of the compound (IV-1).

The amount of compound (IV-2) used in the step of producing compound (IV-3) is preferably 0.7 mol or more and 3 mol or less with respect to 1 mol of compound (IV-1), and is preferably 1 mol or more and 2 mol or less. Is more preferable.

The reaction temperature is preferably 30 ° C. to 180 ° C., more preferably 80 ° C. to 140 ° C. The reaction time is preferably 0.5 hours to 10 hours, more preferably 1 hour to 5 hours.

In the step of producing the compound (IV-4), it is preferable to reflux the compound (IV-3) in an acidic aqueous solution using hydrochloric acid, acetic acid or the like.

The reaction temperature is preferably 30 ° C. to 180 ° C., more preferably 80 ° C. to 140 ° C. The reaction time is preferably 0.5 hours to 10 hours, more preferably 1 hour to 5 hours.

In the step of producing the compound (I), it is preferable to react the compound (IV-4) and the compound (IV-5) in an organic solvent from the viewpoint of yield.
Examples of the organic solvent include those exemplified above, and among these, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and 20 parts by mass or more and 160 parts by mass with respect to 1 part by mass in total of the compound (IV-4) and the compound (IV-5). The following is more preferable.

The amount of the compound (IV-5) used in the step of producing the compound (I) is preferably 0.7 mol or more and 3 mol or less, and 1 mol or more and 2 mol or less with respect to 1 mol of the compound (IV-4). Is more preferable.

The reaction temperature is preferably 30 ° C. to 180 ° C., more preferably 80 ° C. to 140 ° C. The reaction time is preferably 0.5 hours to 10 hours, more preferably 1 hour to 5 hours.

The method for obtaining the target compound (I) from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, a method of filtering the precipitated crystals after cooling can be mentioned. It is preferable that the collected crystals are washed with water or the like and then dried. Further, if necessary, it may be further purified by a known method such as recrystallization or column chromatography.

(Method for producing compound (I) (2))
The compound (I) of the present invention includes compound (IV-2), compound (IV-5), and squaric acid (3,4-dihydroxy-3-cyclobutene-1) represented by the following formula (IV-6). , 2-Zeon) can be produced by a method of reacting with a method.

As the compound (IV-2) and the compound (IV-5), those described above can be used.

In the step of producing the compound (I), it is preferable to adopt a method of dehydrating and condensing the compound (IV-2), the compound (IV-5) and the squaric acid in an organic solvent from the viewpoint of yield. ..
Examples of the organic solvent include those exemplified above, and among these, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, and 20 parts by mass or more and 160 parts by mass with respect to 1 part by mass in total of the compound (IV-4) and the compound (IV-5). The following is more preferable.

The amount of squaric acid used in the step of producing compound (I) is preferably 0.45 mol or more and 0.6 mol or less with respect to 1 mol of the total of compound (IV-2) and compound (IV-5). , 0.47 mol or more and 0.55 mol or less is more preferable.

The reaction temperature is preferably 30 ° C. to 180 ° C., more preferably 80 ° C. to 140 ° C. The reaction time is preferably 1 hour to 20 hours, more preferably 3 hours to 15 hours.

The method for obtaining the target compound (I) from the reaction mixture is not particularly limited, and various known methods can be adopted, and examples thereof include the above-mentioned methods.

(Coloring composition)
The coloring composition of the present invention contains a coloring agent (A) containing compound (I) and a resin (B). The coloring composition may further contain a solvent (E), a leveling agent (F), and the like. In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.

The coloring composition of the present invention has an excellent absorbance retention before and after the light resistance test. The coloring composition is also excellent in heat resistance.

(Colorant (A))
The colorant (A) contained in the coloring composition may contain another dye as the dye (A1) in addition to the compound (I). Examples of such dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. For example, Solvent and Acid in the Color Index (published by The Society of Dyers and Colorists). , Basic, Reactive, Direct, Disperse, Moldant, Bat and other compounds classified as dyes, and known dyes described in dyeing notes (color dyeing company). Further, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes and the like can be mentioned. These dyes may be used alone or in combination of two or more.

Specifically, C.I. I. Solvent Yellow 4 (Hereinafter, the description of CI Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82. , 83, 89, 94, 98, 99, 162;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 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 1, 3, 5, 28, 29, 32, 33; etc. I. Solvent dye,

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 Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Acid Violet 34, 120;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112; etc. I. Acid dye,

C. I. Basic Green 1; etc. I. Basic dye,

C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16; etc. I. Reactive dye,

C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
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 Blue 40; etc. I. Direct dye,

C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60; etc. I. Disperse dye,

C. I. As a moldant dye, C.I. I. Moldant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Moldant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc. C .. I. Moldant dye,

C. I. Bat Green 1 etc. C.I. I. Examples include bat dyes.

The content of the compound (I) in the dye (A1) is preferably 3 parts by mass or more, 100 parts by mass or less, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the total amount of the dye (A1). , 70 parts by mass or less, more preferably 15 parts by mass or more and 50 parts by mass or less. When the content of the compound (I) is within the above range, high color reproducibility can be obtained when the color filter is used, and the thin film tends to be easily formed.

The colorant (A) contained in the coloring composition preferably contains a pigment (A2). The pigment (A2) is not particularly limited, and known pigments can be used. For example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists) can be mentioned, and these can be used alone or in combination of two or more.
Examples of the pigment (A2) include C.I. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,129,137,138, 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;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment Brown 23, 25 and other brown pigments; and C.I. I. Examples thereof include black pigments such as Pigment Black 1 and 7.

As the pigment (A2), 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, 185, 194, 214; C.I. I. Pigment Green 7, 36, 58 and other green pigments are preferred. I. Pigment Yellow 138, 150, 185 and C.I. I. Pigment Green 58 is more preferred. I. Pigment Yellow 138 and C.I. I. Pigment Green 58 is even more preferred. By including the above-mentioned pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment is treated with rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, atomization by a sulfuric acid atomization method, or the like. Treatment, cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out the dispersion treatment by adding a pigment dispersant, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include surfactants, which may be cationic, anionic, nonionic, or amphoteric surfactants. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based surfactants. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, the trade names are KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (BASF). (Manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie) and the like.
When a pigment dispersant is used, the amount used is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the total amount of the pigment (A2). Is. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

When the pigment (A2) is contained, the content ratio of the dye (A1) and the pigment (A2) in the colorant (A) is based on mass, and is usually 45:55 to 1:99, preferably 40: It is 60 to 2:98, more preferably 38:62 to 3:97.

The content of the colorant (A) is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 8 parts by mass or more and 55 parts by mass or less with respect to 100 parts by mass of the solid content of the coloring composition. Yes, more preferably 10 parts by mass or more and 50 parts by mass or less. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the required amount of the resin (B) or the like can be contained in the coloring composition. It tends to be easy to make a thin film. Here, the "solid content" in the present specification means a coloring composition obtained by removing a solvent. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

(Resin (B))
The resin (B) contained in the coloring composition is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (Ba) (hereinafter, may be referred to as "(Ba)") and 2 to 4 carbon atoms. A copolymer with a monomer (Bb) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter, may be referred to as "(Bb)");
Resin [K2]; (Ba), (Bb), and monomer (Bc) copolymerizable with (Ba) (however, different from (Ba) and (Bb)) (hereinafter, "(Bc)" ) ”);
Resin [K3]; Copolymer of (Ba) and (Bc);
Resin [K4]; Resin obtained by reacting (Bb) with a copolymer of (Ba) and (Bc);
Resin [K5]; Resin obtained by reacting (Ba) with a copolymer of (Bb) and (Bc);
Resin [K6]; A resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba) and further reacting with a carboxylic acid anhydride.

Specific examples of (Ba) include unsaturated monocarboxylic acids such as (meth) acrylic 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, 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, 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 and 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 divalent or higher valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Examples thereof include unsaturated (meth) acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, (meth) acrylic 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.

(Bb) is, for example, 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. Say. (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
As used herein, the term "(meth) acrylic acid" refers to at least one of acrylic acid and methacrylic acid. The same applies to the notations such as "(meth) acryloyl" and "(meth) acrylate".

As (Bb), for example, it has a monomer having an oxylanyl 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. Examples include monomers.

As (Bb), a monomer having an oxylanyl group and an ethylenically unsaturated bond is preferable in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further improved. ..

Examples of (Bc) 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 when it is referred to as "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 (Meta) acrylic acid esters such as (meth) 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;
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 (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylnitrile, 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, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are selected from the viewpoint of copolymerization reactivity and heat resistance. preferable.

The resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymers, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Resins such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) ) acrylic acid copolymers, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Decyl acrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer / hydroxy group-containing (meth) acrylate copolymer, 3-methyl-3- (meth) acrylic Resins such as loyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer [K3]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer. Resin to which (meth) acrylate is added, resin such as tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / resin to which glycidyl (meth) acrylate is added to (meth) acrylic acid copolymer [K4]; A resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate ( Resin such as a resin reacted with meta) acrylic acid [K5]; tetrahydrophthalic acid anhydride is further added to a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid. Examples thereof include a resin [K6] such as a resin obtained by reacting an object.
Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable.

For example, the resin [K1] is described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku-Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972). It can be manufactured with reference to the cited references described in.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the copolymer is taken out as a solid (powder) by a method such as reprecipitation. You may use the one. In particular, by using the solvent contained in the coloring composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the coloring composition of the present invention. The manufacturing process of the coloring composition of the above can be simplified.

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 even more preferably 5,000 to 30,000. .. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, 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, and even more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titrating with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 10 to 90 parts by mass, more preferably 20 to 85 parts by mass, and further preferably 30 to 80 parts by mass with respect to 100 parts by mass of the solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to be improved.

(Solvent (E))
The solvent (E) that may be contained in the coloring composition is not particularly limited, and solvents usually used in the art can be used alone or in combination of two or more. For example, 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 in the molecule). Solvent containing -COO- and -O-), 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, dimethylsulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and methyl anisol.

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

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. And so on.

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.

As the solvent, 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, One solvent selected from the group consisting of 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, N, N-dimethylformamide, and tetrahydrofuran, or a combination of two or more. The mixed solvent is preferably one solvent or 2 selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, and tetrahydrofuran. A mixed solvent that combines seeds or more is more preferable.

The content of the solvent (E) is preferably 70 to 95 parts by mass, and more preferably 75 to 92 parts by mass with respect to 100 parts by mass of the coloring composition of the present invention. In other words, the total solid content of the coloring composition is preferably 5 to 30 parts by mass, more preferably 8 to 25 parts by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed.

(Leveling agent (F))
Examples of the leveling agent (F) that may be contained in the coloring composition include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

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

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 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 (F) is preferably 0.0001 parts by mass or more and 0.2 parts by mass or less, and more preferably 0.0002 parts by mass or more and 0.1 parts by mass with respect to 100 parts by mass of the coloring composition. It is 0 parts or less, more preferably 0.0003 parts by mass or more and 0.05 parts by mass or less. The content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

(Other components in the coloring composition)
If necessary, the coloring composition may contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, and light stabilizers.

(Manufacturing method of coloring composition)
The coloring composition can be adjusted, for example, by mixing the coloring agent (a), the resin (B), the solvent (E), and the leveling agent (F) together with other components, if necessary.
It is preferable that the pigment (A2) is mixed with a part or all of the solvent (E) in advance and 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 resin (B) may be blended. The desired coloring composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.
The dye may be dissolved in a part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the colored composition after mixing with a filter having a pore size of about 0.1 to 10 μm.

(Coloring curable resin composition)
The coloring curable resin composition of the present invention contains the above-mentioned coloring composition, the polymerizable compound (C), and the polymerization initiator (D). The color curable resin composition may further contain a polymerization initiator (D1).

The colored curable resin composition of the present invention can be expected to have an excellent absorbance retention rate before and after the light resistance test. The color curable resin composition can be expected to have excellent heat resistance.

(Polymerizable compound (C))
The polymerizable compound (C) contained in the color-curable resin composition is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and is, for example, a polymerizable ethylenically unsaturated bond. Examples thereof include compounds having a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above (Ba). , (Bb) and compounds having one ethylenically unsaturated bond, such as the compounds exemplified as (Bc);
1,6-Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A bis (acryloyloxyethyl) ether and A compound having two ethylenically unsaturated bonds such as 3-methylpentanediol di (meth) acrylate;
Compounds having three ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2- (meth) acryloyloxyethyl) isocyanurate;
It has four ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified pentaerythritol tetra (meth) acrylate. Compound;
Compounds with 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;
Ethylene unsaturated bonds such as dipentaerythritol hexa (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Compound with 6;
Compounds having seven or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and tetrapentaerythritol deca (meth) acrylate; etc. Can be mentioned.
Among them, 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. ..
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly 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) is preferably 7 to 65 parts by mass, more preferably 13 to 60 parts by mass, and further preferably 17 to 55 parts by mass with respect to 100 parts by mass of the solid content. Is. 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.

The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 20:80 to 80:20 on a mass basis. It is 35: 65-80: 20.

(Polymerization initiator (D))
The polymerization initiator (D) contained in the color-curable resin composition 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 is known. A polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound.

The O-acyloxime compound is a compound having a partial structure represented by the formula (Dd1). Hereinafter, * represents a bond.

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-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (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) −Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-Il] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 -On-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and 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-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy is preferable. -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. With these O-acyloxime compounds, a high-brightness color filter tends to be obtained.

The alkylphenone compound is a compound having a partial structure represented by the following formula (Dd2) or a partial structure represented by the following formula (Dd3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (Dd2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morholinophenyl) -2-benzyl butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (Dd3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (Dd2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -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- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. 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.

［式（Ｄｄ４）中、Ｒ^ｄ１〜Ｒ^ｄ５は、置換基を有していてもよい炭素数６〜１０のアリール基を表す。］ Examples of the biimidazole compound include a compound represented by the following formula (Dd4).

[In the formula (Dd4), R ^{d1 to} R ^d5 represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

In the formula (Dd4), examples of the aryl group having 6 to 10 carbon atoms in R ^{d1 to} R ^d5 include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a naphthyl group and the like, and a phenyl group is preferable. Is.
Examples of the substituent that the aryl group having 6 to 10 carbon atoms may have include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include the halogen atoms exemplified in R ^{1 to} R ⁴ in the formula (I). Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl biimidazole and 2,2'-bis (2,3-dichlorophenyl). ) -4,4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl). ) -4,4', 5,5'-tetraphenyl biimidazole, 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 (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4', 5,5'-position is carboalkoxy. Examples thereof include a biimidazole compound substituted with a group (see, for example, Japanese Patent Application Laid-Open No. 7-10913) and the like. Of these, compounds represented by the following formulas and mixtures thereof are preferable.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoin compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, Kinone compounds such as 2-ethylanthraquinone and benzoin; 10-butyl-2-chloroacrydone, benzyl, methylphenylglycoxylate, titanosen compounds and the like can be mentioned. These are preferably used in combination with the polymerization initiator (D1) (particularly amines) described later.

Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, and 4-acetoxy. Onium salts such as phenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate. Species, benzointosylates and the like.

As the polymerization initiator (D), a polymerization initiator that generates an active radical is preferable, and 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. A polymerization initiator containing the above is more preferable, and a polymerization initiator containing an O-acyloxime compound is further preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

(Polymerization initiator (D1))
The polymerization initiator (D1), which may be contained in the color curable resin composition, is a compound or a sensitizer used to promote the polymerization of the polymerizable compound initiated by the polymerization initiator. is there. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and 2-dimethylaminobenzoate. Amino benzoic acid esters such as ethyl, 4-dimethylaminobenzoate 2-ethylhexyl; N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino). ) Bencophenone, alkylaminobenzophenones such as 4,4'-bis (ethylmethylamino) benzophenone; and the like; among them, alkylaminobenzophenone is preferable, and 4,4'-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanic acetic acid, dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfany acetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiator (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

(Other components in the color curable resin composition)
If necessary, the color curable resin composition may contain additives known in the art such as chain transfer agents.

(Manufacturing method of colored curable resin composition)
The coloring curable resin composition can be prepared, for example, by mixing the coloring composition with the polymerizable compound (C), the polymerization initiator (D), the polymerization initiator (D1) and other components. The color curable resin composition is preferably used when patterning is performed by a photolithography method. It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.1 to 10 μm.

(Color filter and its manufacturing method)
The color filter of the present invention can be formed from the above-mentioned coloring composition or coloring curable resin composition. The color filter of the present invention has an excellent absorbance retention before and after the light resistance test. Color filters also have excellent heat resistance.

As a method for producing a color filter formed from a coloring composition or a coloring curable resin composition, for example, a coloring composition or a coloring curable resin composition is applied onto a substrate, and heat-dried (prebaked) and / or reduced pressure. Examples thereof include a method in which volatile components such as a solvent are removed by drying to form a smooth composition layer, and then post-baking is performed. The cured coating film thus formed may be the color filter of the present invention.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit, etc. may be formed on these substrates.

Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.

The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The thickness of the composition layer formed by applying the coloring composition or the coloring curable resin composition is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.
Further, it is preferable to post-bake the obtained composition layer. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

The film thickness of the obtained color filter is not particularly limited and can be appropriately adjusted according to the purpose, application and the like. For example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5. It is ~ 6 μm.

The cured coating film thus obtained can also be patterned by, for example, an etching method.

Using the coloring composition or the coloring curable resin composition of the present invention, a coloring pattern can also be produced by a photolithography method, an inkjet method, a printing method, or the like. Above all, when a color curable resin composition containing the polymerizable compound (C) and the polymerization initiator (D) is used, 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 composition layer, and the deposition composition layer is exposed and developed through a photomask. The coating and drying can be performed under the above-mentioned conditions.

The composition layer is exposed via a photomask to form the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like.
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 composition layer is formed, it is possible to use an exposure device such as a mask aligner and a stepper. preferable.

By bringing the exposed composition layer into contact with a developing solution for development, a colored pattern is formed on the substrate. By development, the unexposed portion of the composition layer is dissolved in a developing solution and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or 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 a paddle method, a dipping method, a 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.

It is preferable to post-bake the obtained coloring pattern. The postbake temperature and time may be the same as the temperature and time described above.

Color filters are preferably used for solid-state image sensors and display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.).

(Optical filter)
Compound (I) can be used, for example, in an optical filter of a display device or the like. The optical filter can be expected to have an excellent absorbance retention before and after the light resistance test. The optical filter can also be expected to have excellent heat resistance.

The optical filter is usually a layer formed from a composition containing a translucent (preferably optically transparent) thermoplastic resin or a thermosetting resin, and can be, for example, a film-like material. Is. The optical filter may have a layer containing the compound (I) (hereinafter, may be referred to as a "color correction layer"), and may be a color correction film having a single-layer structure of the color correction layer. However, it may be a laminated body having a multilayer structure including a color correction layer. When the optical filter has a multi-layer structure, one color correction layer may be included, or two or more color correction layers may be included, and the compound (I) contained in the two or more layers is They may be the same as each other or different from each other.

When the optical filter is a laminated body, the color correction layer may be an adhesive layer or a resin layer other than the adhesive layer (hereinafter, may be simply referred to as a "resin layer"). When the color correction layer is an adhesive layer, the two layers included in the optical filter may be bonded to each other, and the optical filter is used to bond the optical filter to another member such as an image display element. There may be. The adhesive layer can be an adhesive layer formed of an adhesive or an adhesive layer formed of an adhesive.

When the color correction layer is an optical filter (color correction film) having a single-layer structure or a resin layer other than the adhesive layer in an optical filter having a multi-layer structure, the color correction film or the resin layer contains the compound (I). There is no particular limitation on how to make it. For example, [i] a method of kneading with a color correction film or a resin forming a resin layer and heat-molding into a film, [ii] a method of forming a color correction film or a resin layer or a monomer of this resin, and a compound (I). ) Can be dispersed or dissolved in an organic solvent and formed into a film by a casting method or the like. Further, a resin base film coated with a coating liquid obtained by dispersing or dissolving the [iii] compound (I) in a binder resin or an organic solvent may be used as a resin layer, and the resin base film is peeled off from the resin base film. The resulting film may be used as a color correction film. The thickness of the color correction film or the resin layer is not particularly limited, but may be, for example, 1 μm to 200 μm.

When the color correction film or the resin layer contains the compound (I), the content thereof is not particularly limited. For example, the amount of the compound (I) can be 0.001 part by mass or more, preferably 0.02 part by mass or more, with respect to 100 parts by mass of the base polymer forming the color correction film or the resin layer. It is more preferably 05 parts by mass or more, and it can be 10 parts by mass or less, preferably 3 parts by mass or less, and more preferably 0.5 parts by mass or less.

When the color correction layer is an adhesive layer, the method of incorporating the compound (I) into the adhesive layer is also not particularly limited, and when preparing the adhesive composition or the adhesive composition forming the adhesive layer, the compound ( I) may be added. The thickness of the adhesive layer is not particularly limited, but can be, for example, 1 μm to 100 μm.

When the adhesive layer contains the compound (I), the content thereof is not particularly limited. For example, the amount of the compound (I) can be 0.01 part by mass or more, and 0.02 part by mass or more with respect to 100 parts by mass of the base polymer which forms the adhesive and / or the adhesive contained in the adhesive layer. It is preferably 0.05 parts by mass or more, it can be 10 parts by mass or less, it is preferably 5 parts by mass or less, and it is more preferably 0.5 parts by mass or less. preferable.

The optical filter can be used in a display device such as an organic electroluminescence (organic EL) display device or a liquid crystal display device, and can be used by being attached to the visual side of an image display element of this display device. In this case, the optical filter preferably has an adhesive layer and a resin layer other than the adhesive layer, and at least one of the adhesive layer and the resin layer is preferably a color correction layer containing the compound (I).

When the optical filter is a laminated body, the laminated structure thereof is not particularly limited, and for example, it can have the laminated structure shown in FIGS. 1A and 1B. 1A and 1B are schematic cross-sectional views showing an example of an optical filter. The optical filter 10 shown in FIG. 1A can be used in an organic EL display device. The optical filter 10 can include, for example, an adhesive layer 11 for an image display element, a retardation film 12, an adhesive layer 13, a first protective film 14, a polarizing film 15, and a second protective film 16 in this order. The pressure-sensitive adhesive layer 11 and the pressure-sensitive adhesive layer 13 for the image display element all correspond to the above-mentioned adhesive layer, and the retardation film 12, the first protective film 14, the polarizing film 15, and the second protective film 16 all correspond to the above-mentioned adhesive layer. It corresponds to the above-mentioned resin layer.

The first protective film 14, the polarizing film 15, and the second protective film 16 in the optical filter 10 form a polarizing plate, and the first protective film 14 and the second protective film 16 are on the bonding surface side with the polarizing film 15. May have an adhesive layer on the surface. The adhesive layer 11 for an image display element is used for bonding to a light emitting layer including an organic EL element which is an image display element of an organic EL display device. A separator (release film) (not shown) may be provided on the surface of the pressure-sensitive adhesive layer 11 for an image display element on the side opposite to the retardation film 12.

The optical filter 20 shown in FIG. 1B can be used in a liquid crystal display device. The optical filter 20 can include, for example, an adhesive layer 21 for an image display element, a first protective film 24, a polarizing film 25, and a second protective film 26 in this order. The pressure-sensitive adhesive layer 21 for an image display element corresponds to the above-mentioned adhesive layer, and the first protective film 24, the polarizing film 25, and the second protective film 26 all correspond to the above-mentioned resin layer.

The first protective film 24, the polarizing film 25, and the second protective film 26 in the optical filter 20 form a polarizing plate, and the first protective film 24 and the second protective film 26 are on the bonding surface side with the polarizing film 25. May have an adhesive layer on the surface. The adhesive layer 21 for an image display element is used for bonding to a liquid crystal cell which is an image display element of a liquid crystal display device. A separator (release film) (not shown) may be provided on the surface of the pressure-sensitive adhesive layer 21 for an image display element opposite to the first protective film 24.

Compound (I) can be contained in at least one of the resin layer and the adhesive layer forming the optical filters 10 and 20 shown in FIGS. 1 (a) and 1 (b). In the optical filter 10 shown in FIG. 1A, for example, one or more of the pressure-sensitive adhesive layer 11 for an image display element, the pressure-sensitive adhesive layer 13, the first protective film 14, and the second protective film 16 is covered with the above compound ( I) can be included. In the optical filter 20 shown in FIG. 1B, for example, one or more of the pressure-sensitive adhesive layer 21 for an image display element, the first protective film 24, and the second protective film 26 may contain the compound (I). it can.

The optical filters 10 and 20 shown in FIGS. 1 (a) and 1 (b) are merely examples, and may have a laminated structure other than the above. For example, the second protective films 16 and 26 may have a further layer such as a film with an antiglare function or a film with a surface antireflection function on the surface opposite to the polarizing films 15 and 25. Further, the first protective films 14 and 24 may have a function as a retardation film, and the second protective films 16 and 26 have an antiglare function, a surface reflection prevention function, a function as a retardation film and the like. May have. Further, a color correction layer containing the compound (I) may be provided at an arbitrary position in addition to the layers forming the optical filters 10 and 20 shown in FIGS. 1 (a) and 1 (b).

Since the above optical filter contains compound (I), it can be expected to have an excellent absorbance retention rate before and after the light resistance test. The optical filter can be expected to have excellent heat resistance.

Hereinafter, each member forming the optical filter will be described in detail.
(Adhesive layer)
Examples of the adhesive that can be used for the adhesive layer include water-based adhesives, active energy ray-curable adhesives, and combinations thereof. Examples of the water-based adhesive include a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based emulsion adhesive, and the like. The active energy ray-curable adhesive is an adhesive that is cured by irradiating it with active energy rays such as ultraviolet rays, and includes, for example, a polymerizable compound and a photopolymerizable initiator, a photoreactive resin, and the like. Examples thereof include those containing a binder resin and a photoreactive cross-linking agent. Examples of the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable (meth) acrylic monomer, and a photocurable urethane monomer, and oligomers derived from these monomers. Examples of the photopolymerization initiator include substances that generate active species such as neutral radicals, anionic radicals, and cationic radicals by irradiating them with active energy rays such as ultraviolet rays.

As the pressure-sensitive adhesive that can be used for the adhesive layer, a conventionally known pressure-sensitive adhesive can be used. Examples of the adhesive include (meth) acrylic adhesive, urethane adhesive, silicone adhesive, polyester adhesive, polyamide adhesive, polyether adhesive, fluorine adhesive, and rubber adhesive. And so on. Further, it may be an energy ray-curable pressure-sensitive adhesive, a thermosetting pressure-sensitive adhesive or the like. Among these, a (meth) acrylic pressure-sensitive adhesive is preferably used from the viewpoint of transparency, adhesive strength, reliability and the like.

The (meth) acrylic pressure-sensitive adhesive is not particularly limited, but is a polymer containing (meth) acrylic acid ester as a main component (containing 50% by mass or more), and is one type of (meth) acrylic. It may be a homopolymer of an acid ester, or may be a copolymer of a (meth) acrylic acid ester and another (meth) acrylic acid ester or the like. Examples of the (meth) acrylic acid ester include butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic. Examples include 2-phenoxyethyl acid. Further, a polar monomer may be copolymerized with the polymer mainly composed of these (meth) acrylic acids. Examples of the polar monomer include (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, and 2- (N, N-dimethylamino) ethyl ( Examples thereof include monomers having a polar functional group such as a carboxy group, a hydroxyl group, an amide group, an amino group and an epoxy group, such as a meta) acrylate and a glycidyl (meth) acrylate. As the (meth) acrylic resin used for the (meth) acrylic pressure-sensitive adhesive, a resin having a weight average molecular weight (Mw) of 100,000 or more can be used, preferably 600,000 or more, and usually 2.5 million or less. is there.

These (meth) acrylic pressure-sensitive adhesives can be used alone, but are usually used in combination with a cross-linking agent. Examples of the cross-linking agent include divalent or polyvalent metal ions that form a carboxylic acid metal salt with a carboxy group, and amine compounds that form an amide bond with a carboxy group. Examples thereof include epoxy compounds and diol compounds that form an ester bond with a carboxy group, and isocyanate compounds that form an amide bond with a carboxy group. Of these, isocyanate compounds are preferably used.

Among isocyanate compounds, xylylene diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate; adducts obtained by reacting these isocyanate compounds with polyols such as glycerol and trimethylpropan; these isocyanate compounds are dimerized and trimeric. Etc. or a mixture thereof; a mixture of two or more kinds of the isocyanate-based compounds listed above is preferably used.
Suitable isocyanate compounds include tolylene diisocyanate, adducts obtained by reacting tolylene diisocyanate with polyol, dimer of tolylene diisocyanate, and trimeric of tolylene diisocyanate, and hexamethylene diisocyanate and hexamethylene diisocyanate. Examples thereof include an adduct compound obtained by reacting a polyol, a hexamethylene diisocyanate dimer, and a hexamethylene diisocyanate trimeric.

The content of the cross-linking agent in the acrylic pressure-sensitive adhesive is usually 0 parts by mass or more and 5 parts by mass or less, preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic resin. ..

The acrylic pressure-sensitive adhesive can further contain a silane compound. When the acrylic pressure-sensitive adhesive contains a silane compound, the adhesion between the obtained pressure-sensitive adhesive layer and an optical member such as a glass substrate can be improved.

Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl. Methyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Examples thereof include sidoxylpropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane and the like. Two or more kinds of silane compounds may be used.

The silane compound may be of the silicone oligomer type. When the silicone oligomer is shown in the form of a (monomer) oligomer, for example, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane Examples thereof include −tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetramethoxysilane copolymer and the like.

The content of the silane compound in the pressure-sensitive adhesive composition is usually 0.01 part by mass or more and 10 parts by mass or less, preferably 0.05 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the (meth) acrylic resin. More preferably, it is 0.1 part by mass or more and 2 parts by mass or less. When the content of the silane compound is 0.01 parts by mass or more, the effect of improving the adhesion between the pressure-sensitive adhesive layer and the optical member such as a glass substrate can be easily obtained. Further, when the content of the silane compound is 10 parts by mass or less, bleeding out of the silane compound from the pressure-sensitive adhesive layer can be suppressed.

The acrylic pressure-sensitive adhesive may further contain an ionic compound as an antistatic agent for imparting antistatic properties. The ionic compound is a compound having an inorganic cation or an organic cation and an inorganic anion or an organic anion. The acrylic pressure-sensitive adhesive may contain two or more kinds of ionic compounds.

Examples of the inorganic cation include alkali metal ions such as lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], potassium cation [K ⁺ ], beryllium cation [Be ²⁺ ], magnesium cation [Mg ²⁺ ], and calcium cation. Examples thereof include alkaline earth metal ions such as [Ca ²⁺ ].
Examples of the organic cation include imidazolium cation, pyridinium cation, pyrrolidinium cation, ammonium cation, sulfonium cation, phosphonium cation and the like.

The inorganic anion, e.g., chloride anion [Cl ^-], bromide anion [Br ^-], iodide anion [I ^-], tetrachloro aluminate anions [AlCl ₄ ^-], hepta-chloro-di aluminate anion _[Al 2 Cl ₇ ^-], tetrafluoroborate anion [BF ₄ ^-], hexafluorophosphate anion [PF ₆ ^-], perchlorate anion [ClO ₄ ^-], nitrate anion [NO ₃ ^-], hexafluoro ah cell anion [AsF ₆ ^-], hexafluoroantimonate anion [SbF ₆ ^-], hexafluoro niobate anions [NbF ₆ ^-], hexafluoro tantalate anion [TaF ₆ ^-], dicyanamide anion _[(CN) 2 N ^-] and the like include Be done.

Examples of the organic anion include acetate anion [CH ₃ COO ⁻ ], trifluoroacetate anion [CF ₃ COO ⁻ ], methanesulfonate anion [CH ₃ SO ₃ ⁻ ], trifluoromethanesulfonate anion [CF ₃ SO ₃ ⁻ ], and the like. p-Toluene sulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ], bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N ⁻ ], bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂₎ ) ₂ N ^-], tris (trifluoromethanesulfonyl) meth acetonide anion _{[(CF 3 SO 2) 3 C} - ], dimethyl phosphinate anion _{[(CH 3)} 2 POO ^-], (poly) hydrofluoroether fluoride anion [ F _{(HF) n} ^-] (n is about 1 to 3), thiocyanate anion [SCN ^-], perfluorobutane sulfonate anion _[C 4 _F 9 SO ₃ ^-], bis (pentafluoroethane sulfonyl) imide anion [( C ₂ F ₅ SO ₂ ) ₂ N ⁻ ], perfluorobutanoate anion [C ₃ F ₇ COO ⁻ ], (trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imide anion [(CF ₃ SO ₂ ) (CF ₃ CO) ) N ^-], and the like.

Specific examples of the ionic compound can be selected from the combination of the above-mentioned cationic component and anionic component.

Examples of ionic compounds having an organic cation include N-octylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-butyl-4-methylpyridinium hexafluorophosphate, N-decylpyridinium bis ( Pyridinium salts such as fluorosulfonyl) imide, N-hexylpyridinium bis (trifluoromethanesulfonyl) imide, N-octylpyridinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl- 3-Methyl imidazolium p-toluenesulfonate, 1-ethyl-3-methyl imidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methyl Imidazolium salts such as imidazolium methanesulfonate; N-butyl-N-methylpyrrolidinium hexafluorophosphate, N-butyl-N-methylpyrrolidinium bis (fluorosulfonyl) imide, N-butyl-N-methylpyrrolidi Pyrrolidinium salts such as nium bis (trifluoromethanesulfonyl) imide; quaternary ammonium salts such as tetrabutylammonium hexafluorophosphate and tetrabutylammonium p-toluenesulfonate.

Examples of ionic compounds having an inorganic cation include lithium bromide, lithium iodide, sodium hexafluorophosphate and the like.

The ionic compound is preferably solid at room temperature from the viewpoint of maintaining antistatic performance. The ionic compound preferably has a melting point of 30 ° C. or higher, more preferably 35 ° C. or higher. On the other hand, if the melting point is too high, the compatibility with the (meth) acrylic resin deteriorates. Therefore, the melting point of the ionic compound is preferably 90 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 50. It is below ° C.

The content of the ionic compound in the acrylic pressure-sensitive adhesive is preferably 0.1 part by mass or more and 8 parts by mass or less, and more preferably 0.2 parts by mass or more and 6 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin. Parts or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less, and particularly preferably 1 part by mass or more and 5 parts by mass or less. A content of the ionic compound of 0.1 parts by mass or more is advantageous for improving the antistatic performance, and a content of 8 parts by mass or less is advantageous for maintaining the durability of the pressure-sensitive adhesive layer.

Various additives may be further blended in the adhesive and the pressure-sensitive adhesive. Examples of the additive include a reworking agent, a tackifier resin, an antioxidant, an ultraviolet absorber, an antifoaming agent, a corrosive agent, a light diffusing agent such as fine particles, and the like.

(Resin layer)
As the resin layer, a polarizing film as a linear polarizing film; a protective film provided to protect the surface of a polarizing film or the like; a retardation film; an optical compensation film other than the retardation film; an antiglare function having an uneven shape on the surface. Attached film, film with surface antireflection function; reflective film having a reflective function on the surface; semitransmissive reflective film having both reflective function and transmissive function; light diffusing film; hard coat film; color correction film and the like. The optical filter may include one or more of the above-mentioned resin layers.

Examples of the polarizing film include those in which iodine is oriented in the polyvinyl alcohol-based resin layer, those in which the liquid crystal compound and the dichroic dye are oriented, and the like.

The material when the resin layer is other than the polarizing film is not particularly limited, but for example, a chain polyolefin resin (polyethylene resin, polypropylene resin, etc.), a cyclic polyolefin resin (norbornen resin, etc.), etc. Polyethylene resin; Cellulose ester resin such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; Polyester resin such as polyethylene terephthalate and polyethylene naphthalate; Polycarbonate resin; (Meta) acrylic acid, Poly (meth) acrylic Examples thereof include (meth) acrylic resins such as methyl acid acid; vinyl alcohol-based resins such as polyvinyl alcohol and polyvinyl acetate; polystyrene-based resins; mixtures and copolymers thereof. These resins contain one or more additives such as lubricants, plasticizers, dispersants, heat stabilizers, ultraviolet absorbers, infrared absorbers, antistatic agents, antioxidants, and light diffusers such as fine particles. It may be contained.

(Display device)
The above-mentioned color filter and optical filter can be suitably used for display devices such as organic EL display devices, liquid crystal display devices, inorganic electroluminescence (inorganic EL) display devices, electron emission display devices, and electronic paper.

2 (a) and 2 (b) are schematic cross-sectional views showing an example of a display device provided with an optical filter. The display device shown in FIG. 2A is an organic EL display device including the optical filter 10 shown in FIG. 1A and an image display element 1 which is a light emitting layer including an organic EL element. The optical filter 10 can be arranged on the visual side of the image display element 1 via the adhesive layer 11 for the image display element.

The display device shown in FIG. 2B is a liquid crystal display device including the optical filter 20 shown in FIG. 1B and an image display element 2 which is a liquid crystal cell including a liquid crystal layer. The optical filter 20 can be arranged on the visual side of the image display element 2 via the adhesive layer 21 for the image display element.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" in Examples, Comparative Examples, Application Examples, and Comparative Application Examples are parts by mass.

[Identification of compound]
The structure of the compound was identified by mass analysis (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[Example 1 (Compound (I))]
3,4-Dibutoxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.00 parts (110.5 mmol), 1-butanol represented by the following formula (IV-1-a). After heating and stirring 82 parts (1.1 mol) at 110 ° C., 3-ethyl-2,4-dimethylpyrrole represented by the following formula (IV-2-a) (manufactured by Tokyo Chemical Industry Co., Ltd.) 13. 61 parts (110.5 mmol) were added dropwise over 10 minutes, and the mixture was heated under reflux for 3 hours. When the mixture was cooled to room temperature after the reaction, crystals were precipitated, so filtration was performed to separate the solution from the precipitate. When repulp was carried out on the precipitate using 500 mL of hexane, a light green powder (a compound represented by the following formula (IV-3-a)) was obtained.

The powder obtained above was poured into an aqueous solution prepared with 12.6 mL of concentrated hydrochloric acid and 84.0 mL of distilled water using 110.0 mL of acetic acid, and heated under reflux at 110 ° C. for 2 hours, from pale green to pale orange. A color change occurred and the reaction stopped. The reaction mixture was cooled to room temperature, the pale orange powder was filtered off, and then the repulp was washed with 500 mL of hexane. As a result, the pale yellow compound represented by the following formula (IV-4-a) was 18.34. Part (yield 75.7%) was obtained.

0.5 part (2.3 mmol) of the obtained compound represented by the formula (IV-4-a), 0.32 part (2.5 mmol) of phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1- 6.8 parts of butanol and 53 parts of toluene were mixed. The resulting mixture was stirred at a temperature of 110 ° C. for 3 hours while removing the water produced using a Dean-Stark tube. After completion of the reaction, the mixture was cooled to room temperature to obtain a precipitate. Therefore, the precipitate was separated by filtration, and the repulp was washed with 100 mL of hexane and 100 mL of methanol. The red powder was a compound represented by the following formula (A-1). (Hereinafter, it may be referred to as “compound (A-1)”), and 0.61 part (yield 81%) was obtained. Mass spectrometry was performed on the obtained compound (A-1).
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 328.3
Exact Mass: 327.1

[Comparative Example 1]
3,4-Dihydroxy-3-cyclobutene-1,2-dione (squaric acid) (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 1 part (8.8 mmol) represented by the following formula (IV-6), above. 3-Ethyl-2,4-dimethylpyrrole (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.16 parts (17.5 mmol) and 1-butanol 33 parts (0.4 mol) represented by the formula (IV-2-a). ) And 55.2 parts (0.6 mol) of toluene were mixed. The resulting mixture was stirred at a temperature of 110 ° C. for 3 hours while removing the water produced using a Dean-Stark tube. After completion of the reaction, the solvent in the reaction solution was distilled off, 220 parts of ion-exchanged water was added, and the precipitated crude product was collected by filtration.

The obtained crude product may be referred to as a compound represented by the formula (B-1) (hereinafter referred to as “compound (B-1)”) by using column chromatography (developing solvent chloroform) using silica gel. ) Was separated and then dried under reduced pressure at a temperature of 60 ° C. for 12 hours to obtain 2.4 parts of compound (B-1). Mass spectrometry was performed on the obtained compound (B-1).
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 325.5
Exact Mass: 324.2

[Example 2 (coloring composition)]
(Synthesis of resin (B1))
After 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, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C. with stirring. .. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] deca-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] ^{. 6} ] A mixed solution of 25 parts of a mixture of deca-9-ylacrylate (content ratio 1: 1), 137 parts of cyclohexyl maleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. did. On the other hand, a mixed solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B1)) solution having a B-type viscosity (23 ° C.) of 23 mPas and a solid content of 25.6%. The weight average molecular weight Mw of the produced copolymer was 8000, the solid content acid value was 111 mg-KOH / g, and the dispersity was 2.1. The resin (B1) has the following structural units.

(Preparation of coloring composition)
The coloring composition (a-1) was obtained by mixing the following components.
Colorant (A): Compound (A-1) 0.10 parts Resin (B): Resin (B1) 10.86 parts Solvent (E): Tetrahydrofuran 68.18 parts Solvent (E): Propylene glycol monomethyl ether acetate
20.82 parts Leveling agent (F): Polyether-modified silicone oil (solid content equivalent) (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.006 parts

(Preparation of colored coating film)
The coloring composition (a-1) 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 composition layer. Then, it was post-baked in an oven at 230 ° C. for 3 minutes to obtain a colored coating film (a-1). A light resistance test was conducted using the obtained colored coating film (a-1). The results are shown in Table 1.

[Light resistance test]
An ultraviolet cut filter (COLORED OPTICAL GLASS L38, manufactured by Hoya Co., Ltd., which cuts light of 380 nm or less) is placed on the obtained colored coating film (a-1), and a light resistance tester (Suntest CPS +, It was irradiated with xenon lamp light for 24 hours at Toyo Seiki Co., Ltd.). Before and after light irradiation, the absorbance of the colored coating film (a-1) at the maximum absorption wavelength was measured, and the absorbance after light irradiation was calculated with the absorbance before light irradiation as 100%. The maximum absorption wavelength of the colored coating film (a-1) is shown in Table 1.

[Heat resistance test]
The obtained colored coating film (a-1) was heated in an oven at 230 ° C. for 20 minutes. Before and after heating, the absorbance of the colored coating film (a-1) at the maximum absorption wavelength was measured, and the absorbance after heating was calculated with the absorbance before heating as 100%. As a result, the absorbance of the colored coating film (a-1) after heat resistance was 72%.

[Comparative Example 2]
A coloring composition (b-1) was obtained in the same manner as in Example 1 except that 0.10 part of compound (B-1) was used instead of compound (A-1). Further, a colored coating film (b-1) was obtained in the same manner as in Example 1 except that this coloring composition (b-1) was used. Using the obtained colored coating film (b-1), a light resistance test was conducted in the same procedure as in Example 2. The results are shown in Table 1.

As shown in Table 1, the coloring composition containing the compound (I) has an excellent absorbance retention before and after the light resistance test.

1,2 image display element, 10 optical filter, 11 adhesive layer for image display element, 12 retardation film, 13 adhesive layer, 14 first protective film, 15 polarizing film, 16 second protective film, 20 optical filter, 21 Adhesive layer for image display element, 24 1st protective film, 25 polarizing film, 26 2nd protective film.

Claims (5)

A compound represented by the formula (I).

[In formula (I),
Q is
Equation (Q1): * -CR ⁶ = CR ^5- NR ³ -**,
Equation (Q2): * -O-CR ⁵ = N-**,
Equation (Q3): * -S-CR ⁵ = N-**,
Equation (Q4): * -N = CR ^5- NR ³ -**, or Equation (Q5): * -NR ⁶ -CR ⁵ = N-**
Represents a group represented by (* represents a bond with a carbon atom to which R ⁴ is bonded).
R ^{1 to} R ⁵ each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a hydrogen atom or a substituent, and are contained in the hydrocarbon group −CH ₂ −. May be replaced with -O- or -CO-.
R ⁶ represents a monovalent aromatic group which may have a substituent or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and the fat. -CH _2- contained in the group hydrocarbon group may be replaced with -O- or -CO-. ] A coloring composition containing a colorant containing the compound according to claim 1 and a resin. A coloring curable resin composition containing the coloring composition according to claim 2, a polymerizable compound, and a polymerization initiator. A color filter formed from the coloring composition according to claim 2 or the coloring curable resin composition according to claim 3. A display device including the color filter according to claim 4.

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