TWI753043B - Compound, coloring resin composition having the compound, color filter formed by the coloring resin composition and display device having the color filter - Google Patents

Abstract

Photostability of current color filters formed by current known coloring resin composition cannot sufficiently satisfy the needs. The present invention relates to a compound, a coloring resin composition having the compound, a color filter formed by the coloring resin composition and a display device having the color filter. The compound of the present invention is represented by formula (1) as shown below:

Description

Compound, colored resin composition containing the compound, color filter formed from the colored resin composition, and display device containing the color filter

The present invention relates to a compound, a colored resin composition containing the compound, a color filter formed from the colored resin composition, and a display device including the color filter.

Colored resin compositions are used in the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored resin composition, a colored resin composition containing a compound represented by the following formula as a colorant is known.

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2013-50693

A color filter formed from a conventionally known colored resin composition containing the above-mentioned compound may not have sufficient light resistance.

That is, the present invention includes the following inventions.

[1] A compound represented by formula (1).

[式(1)中，R¹至R⁴相互獨立地表示氫原子、可具有取代基的碳數1至20的飽和烴基或者可具有取代基的碳數6至10的芳香族烴基，其中至少一個表示具有烷氧基作為取代基的碳數6至10的芳香族烴基，該飽和烴基中所含的-CH₂-可被替換為-O-、-CO-或-NR⁵-。R¹及R²可一起形成含有氮原子的環，R³及R⁴可一起形成含有氮原子的環。

[In formula (1), R ¹ to R ⁴ independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein at least One represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkoxy group as a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ⁵ -. R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

R ⁵ to R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

[2] The compound according to [1], wherein R ¹ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkoxy group as a substituent, and R ² to R ⁴ independently of each other represent optionally substituted A saturated hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, or R ¹ and R ³ represent an aromatic hydrocarbon group having an alkoxy group as a substituent having a carbon number of 6 to 10, and R ² and R ⁴ independently of each other represent a substituted group A saturated hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom.

[3] The compound according to [1] or [2], wherein the aromatic hydrocarbon group having 6 to 10 carbon atoms and having an alkoxy group is a group represented by formula (1x).

[式(1x)中，R⁸表示碳數1至8的烷基。＊表示與氮原子的鍵結端。]

[In formula (1x), R ⁸ represents an alkyl group having 1 to 8 carbon atoms. * indicates a bond terminal with a nitrogen atom. ]

[4] The compound according to [3], wherein R ⁸ is methyl, ethyl, n-propyl, isopropyl or butyl.

[5] A colored resin composition comprising the compound and resin according to any one of [1] to [4].

[6] A color filter formed of the colored resin composition according to [5].

[7] A display device including the color filter described in [6].

The colored resin composition can form a color filter excellent in light resistance by including the compound of the present invention as a colorant.

The compound of the present invention is represented by formula (1). Hereinafter, the compound represented by formula (1) may be referred to as "compound (1)". The compounds of the present invention also include tautomers and salts thereof. In addition, each component and functional group exemplified below can be used individually or in combination.

[In formula (1), R ¹ to R ⁴ independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein at least One represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkoxy group as a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -NR ⁵ -. R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

R ⁵ to R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.

The above-mentioned alkoxy group is preferably a group represented by -OR ⁸ .

R ⁸ represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

Examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , and -CO ₂ H , -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , or -SO ₂ NR ⁹ R ¹⁰ , preferably these substituents are substituted with a hydrogen atom contained in an aromatic hydrocarbon group. Among these, the substituents are preferably -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ , more preferably -OR ⁸ and -SO ₃ ^- Z ⁺ , -SO ₂ NR ⁹ R ¹⁰ . As -SO ₃ ^- Z ⁺ in this case, -SO ₃ ^-+ N(R ¹¹ ) ₄ is preferred.

Here, Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ^11s may be the same or different.

R ⁹ and R ¹⁰ independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, - NH- or -NR ⁸ -, R ⁹ and R ¹⁰ may combine with each other to form a nitrogen atom-containing 3- to 10-membered heterocyclic ring.

R ¹¹ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Examples of saturated hydrocarbon groups having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ include methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, Heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2 - Branched chain alkyl groups such as ethylhexyl; alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

The hydrogen atom contained in the saturated hydrocarbon group in R ¹ to R ⁴ may be substituted, for example, with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom of the saturated hydrocarbon group of R ¹ to R ⁴ can be substituted include those exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ . The same base.

The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxyl group or a halogen atom as a substituent.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include, for example, the following rings. In the formula, * represents a bond terminal.

Examples of -OR ⁸ include methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2- Alkoxy groups such as ethylhexyloxy and eicosyloxy, etc.

Examples of -CO ₂ R ⁸ include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl. Wait.

Examples of -SR ⁸ include alkylthio groups such as methylthio, ethylthio, butylthio, hexylthio, decylthio, and eicosylthio.

Examples of -SO ₂ R ⁸ include alkanes such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl Sulfonyl, etc.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and a dioxysulfonyl group. Decyloxysulfonyl and other alkoxysulfonyl groups and the like.

Examples of -SO ₂ NR ⁹ R ¹⁰ include sulfamoyl; N-methyl sulfamoyl, N-ethyl sulfamoyl, N-propyl sulfamoyl, N-isopropyl N-butylaminosulfonyl, N-butylaminosulfonyl, N-isobutylaminosulfonyl, N-2-butylaminosulfonyl, N-tert-butylaminosulfonyl, N-pentane sulfamoyl, N-(1-ethylpropyl) sulfamoyl, N-(1,1-dimethylpropyl) sulfamoyl, N-(1,2-dimethylpropyl) base) sulfamoyl, N-(2,2-dimethylpropyl) sulfamoyl, N-(1-methylbutyl) sulfamoyl, N-(2-methylbutyl) Sulfamoyl, N-(3-methylbutyl) sulfamoyl, N-cyclopentyl sulfamoyl, N-hexyl sulfamoyl, N-(1,3-dimethylbutyl) ) sulfamoyl, N-(3,3-dimethylbutyl) sulfamoyl, N-heptyl sulfamoyl, N-(1-methylhexyl) sulfamoyl, N-( 1,4-Dimethylpentyl) sulfamoyl, N-octyl sulfamoyl, N-(2-ethylhexyl) sulfamoyl, N-(1,5-dimethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl, N-(1,1,2,2-tetramethylbutyl) sulfamoyl; N,N-dimethylsulfamoyl, N, N-ethylmethylaminosulfonyl, N,N-diethylaminosulfonyl, N,N-propylmethylaminosulfonyl, N,N-isopropylmethylaminosulfonyl, N,N-tert-butylmethylsulfamoyl, N,N-butylethylsulfamoyl, N,N-bis(1-methylpropyl)sulfamoyl, N,N-heptyl N,N-2-substituted sulfamoyl, etc., methyl sulfayl, etc.

R ⁵ is preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ , more preferably Preferably -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ .

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁵ to R ⁷ include the alkyl group having 1 to 6 carbon atoms in the above-mentioned alkyl groups. As one of R ⁶ and R ⁷ , a hydrogen atom is preferred.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, a phenylbutyl group, and the like.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

The above-mentioned ⁺ N(R ¹¹ ) ₄ is preferably a saturated hydrocarbon group having 5 to 20 carbon atoms in at least two of the four R ^11s . Moreover, 20-80 are preferable and, as for the total carbon number of ⁴ R11, 20-60 are more preferable.

In the compound (1), preferably R ¹ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkoxy group as a substituent, and R ² to R ⁴ independently represent 1 to 20 carbon atoms which may have a substituent A saturated hydrocarbon group or a hydrogen atom, or R ¹ and R ³ represent an aromatic hydrocarbon group having an alkoxy group as a substituent with a carbon number of 6 to 10, and R ² and R ⁴ independently of each other represent a carbon number 1 that may have a substituent to 20 saturated hydrocarbon groups or hydrogen atoms.

As the aromatic hydrocarbon group having 6 to 10 carbon atoms having the above-mentioned alkoxy group, a group represented by the formula (1x) is preferable.

[In formula (1x), R ⁸ represents an alkyl group having 1 to 8 carbon atoms. * indicates a bond terminal with a nitrogen atom. ]

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁸ include the above-mentioned alkyl group having 1 to 8 carbon atoms in R ⁸ , preferably methyl, ethyl, n-propyl, and isopropyl. or butyl, more preferably methyl or isopropyl.

The compound (1) is preferably a compound represented by the formula (2) (hereinafter sometimes referred to as "compound (2)"). Compound (2) may be its tautomer.

[In the formula (2), R ²¹ to R ²⁴ independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, at least one of which represents an alkoxy group as a substituent Aromatic hydrocarbon group having 6 to 10 carbon atoms. R ²¹ and R ²² together may form a nitrogen atom-containing ring, and R ²³ and R ²⁴ may together form a nitrogen atom-containing ring.

R ²⁶ represents a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ include the same groups as those listed as the aromatic hydrocarbon group for R ¹ to R ⁴ above. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ¹⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

Examples of the above-mentioned alkoxy group include the same groups as -OR ⁸ exemplified as a substituent of the aromatic hydrocarbon group represented by R ¹ , and preferably a methoxy group, an ethoxy group, an n-propoxy group, and an isopropyl group. oxy or butoxy, more preferably methoxy or isopropoxy.

Examples of the nitrogen atom-containing ring formed by R ²¹ and R ²² together and the nitrogen atom-containing ring formed by R ²³ and R ²⁴ together include the same nitrogen atom-containing rings as the ring formed by R ¹ and R ² together. . Among them, an aliphatic heterocycle is preferred. Examples of the aliphatic heterocycle include the following aliphatic heterocycles. In the formula, * represents a bond terminal.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ include the same groups as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are -R ²⁶ , it is preferable that -R ²⁶ is each independently a methyl group or an ethyl group. In addition, as one of R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ , it is preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, Still more preferred is 2-ethylhexyl.

In the compound (2), preferably R ²¹ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkoxy group as a substituent, and R ²² to R ²⁴ independently represent a hydrogen atom or -R ²⁶ , or R ²¹ and R ²³ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkoxy group as a substituent, and R ²² and R ²⁴ independently represent a hydrogen atom or -R ²⁶ .

As the aromatic hydrocarbon group having 6 to 10 carbon atoms having the above-mentioned alkoxy group, a group represented by the formula (1x) is preferable.

In addition, as the compound (1), a compound represented by the formula (3) (hereinafter sometimes referred to as "compound (3)") is also preferable. Compound (3) may be its tautomer.

[In formula (3), R ³¹ and R ³² independently represent a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group of these R ³¹ and R ³² may be replaced by an aromatic group having 6 to 10 carbon atoms. Hydrocarbon group or halogen atom substitution, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ - contained in the saturated hydrocarbon group of the above R ³¹ and R ³² may be replaced by -O-, -CO- or -NR ¹¹ -.

R ³³ and R ³⁴ independently represent an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms or an alkoxy group, at least one of which represents an alkyl group Oxygen.

R ³¹ and R ³³ together may form a nitrogen atom-containing ring, and R ³² and R ³⁴ may together form a nitrogen atom-containing ring.

p and q represent an integer of 0 to 5 independently of each other. When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different. However, the sum of p and q is 1 or more.

R ¹¹ has the same meaning as above. ]

Examples of the saturated hydrocarbon groups having 1 to 10 carbon atoms in R ³¹ and R ³² include groups having 1 to 10 carbon atoms among the saturated hydrocarbon groups in R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which can be substituted as a substituent include the same groups as those in R ¹ .

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

Preferably, R ³¹ and R ³² are independently a saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl Wait.

Examples of the alkylthio group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, an isopropylthio group, and the like.

Examples of the alkylsulfonyl groups having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, and isopropyl. Sulfonyl, etc.

Examples of the alkoxy group in R ³³ and R ³⁴ include the same groups as -OR ⁸ exemplified as the substituent of the aromatic hydrocarbon group represented by R ¹ , and preferably methoxy, ethoxy, normal Propoxy, isopropoxy or butoxy, more preferably methoxy or isopropoxy.

As R ³³ and R ³⁴ , an alkyl group or an alkoxy group having 1 to 4 carbon atoms is preferable, and a methyl group or an alkoxy group is more preferable.

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

In the compound (3), at least one of R ³³ and R ³⁴ is an alkoxy group, and preferably, R ³³ and R ³⁴ are an alkoxy group.

Compound (3) is preferably a compound represented by formula (3-1).

[In formula (3-1), R ³¹ and R ³² have the same meaning as described above. R ³⁸ and R ³⁹ independently represent an alkyl group having 1 to 8 carbon atoms. ]

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ³⁸ and R ³⁹ include the above-mentioned groups having 1 to 8 carbon atoms in R ⁸ , preferably methyl, ethyl, n-propyl, isopropyl propyl or butyl, more preferably methyl or isopropyl.

Examples of the compound (1) include compounds (I-1) to (I-504) represented by the formula (I).

Wherein, H represents a hydrogen atom, Me represents methyl, Et represents ethyl, Pr represents n-propyl, iPr represents 2-propyl, Bu represents n-butyl, 2EH represents 2-ethylhexyl, (p1) to (p8 ) respectively represent the following bases. In the formula, * represents a bond terminal.

(h1) to (h4) respectively indicate that R ^3a and R ^4a together form the following ring. In the formula, * represents a bond terminal.

As compound (1), compounds (I-1) to (I-14), compounds (I-57) to (I-112), and compounds (I-113) to (I-168) are preferred.

As a method for producing the compound (1), the compound represented by the formula (1x), the compound represented by the formula (1z-1), and the compound represented by the formula (1z-2) can be mentioned in the presence of an organic solvent Or the method of reaction without solvent. The reaction temperature is preferably 30°C to 180°C, more preferably 50°C to 110°C. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

[In formula (1x), formula (1z-1), formula (1z-2) and formula (1), R ¹ to R ⁷ have the same meanings as above, respectively. ]

Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; Ketone solvents such as isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone, etc.

The usage-amount of the compound represented by the formula (1z-1) and the compound represented by the formula (1z-2) is preferably 1 mol or more with respect to 1 mol of the compound represented by the formula (1x) and 8 mol or less, more preferably 1 mol or more and 5 mol or less. Each of them may be reacted in stages, or they may be reacted simultaneously.

When compound (1) is a compound in which any one of R ¹ to R ⁴ is a hydrogen atom (hereinafter sometimes referred to as "compound (1a)"), compound (1a) can be prepared in the presence or absence of an organic solvent. ) is further reacted with the compound represented by the formula (1z-3). The reaction temperature is preferably 30°C to 180°C, more preferably 50°C to 110°C. The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

R ¹² -Br (1z-3)

[In formula (1z-3), R ¹² represents an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms. ]

As said organic solvent, the same solvent as the solvent exemplified as the organic solvent when compound (1x) and compound (1z-1) and (1z-2) are made to react can be mentioned.

When the compound (1a) is reacted with the compound represented by the formula (1z-3), a basic substance such as sodium carbonate and potassium carbonate may coexist.

The method of obtaining the compound (1) which is the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with water, and the precipitated crystals can be collected by filtration. The temperature at the time of mixing the reaction mixture with water is preferably 10°C or higher and 50°C or lower. In addition, after that, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like, and then dried. In addition, if necessary, it can be further purified by a known method such as recrystallization.

The colored resin composition of the present invention contains the compound (1) and a resin.

The content of the compound (1) is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 1 to 20 parts by mass relative to 100 parts by mass of the resin.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (maybe the following). Resin of the structural unit referred to as "(a)"). The resin (B) preferably further has a structural unit derived from the monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, The structural unit and side chain derived from the monomer (c) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)") which can be copolymerized with (a) have ethylenically unsaturated bonds At least one structural unit selected from the group consisting of the structural units.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-( Meth)acryloyloxyethyl]ester, etc., preferably acrylic acid, methacrylic acid, maleic anhydride.

(b) preferably has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and (methyl) base) acryloxy monomer.

In addition, in this specification, "(meth)acrylic acid" represents at least 1 type chosen from the group which consists of acrylic acid and methacrylic acid. Symbols such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane (meth)acrylate. ester, 3-ethyl-3-(meth)acryloyloxymethyl oxetane, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (meth)acrylate base) 3,4- ^{epoxytricyclo} [5.2.1.02,6]decyl acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane.

Examples of (c) include methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (meth)acrylate (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N- ^{phenylmaleimide} , N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene, etc., preferably styrene, vinyltoluene, N-phenylmaleimide , N-cyclohexylmaleimide, N-benzylmaleimide, etc.

A resin having a structural unit having an ethylenically unsaturated bond in a side chain can be obtained by adding (b) to the copolymer of (a) and (c), or adding (a) to (b) and (c) ) of the copolymer. This resin may be a resin obtained by adding (a) to the copolymer of (b) and (c), and further reacting a carboxylic acid anhydride.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and even more preferably from 5,000 to 30,000.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g in terms of solid content. 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 titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65 mass %, more preferably 13 to 60 mass %, and still more preferably 17 to 55 mass % with respect to the total amount of solid content.

<Colorant (A)>

The colored resin composition of the present invention may contain a dye (A1) and a pigment (A2) as a colorant (A) in addition to the compound (1).

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as substances having a hue other than pigments in the splendor index (published by The Society of Dyers and Colourists), and well-known dyes described in the Dyeing Note (Shiyesha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azo dyes can be mentioned. Methylene dyes, squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes, etc. Of these, organic solvent-soluble dyes are preferred. Moreover, as a dye, the dyes described in Unexamined-Japanese-Patent No. 2015-28121, Unexamined-Japanese-Patent No. 2013-7032, Unexamined-Japanese-Patent No. 2013-144724, and Unexamined-Japanese-Patent No. 2013-53292 are also preferable.

It does not specifically limit as a pigment (A2), A well-known pigment can be used, For example, the pigment classified as a pigment in a color index (published by The Society of Dyers and Colourists) is mentioned.

Examples of pigments include CI 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, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments, etc.

When the colored resin composition of the present invention is a blue colored resin composition, the pigment is preferably at least one selected from the group consisting of blue pigments and purple pigments.

When the colored resin composition of the present invention is a red colored resin composition, the pigment is preferably at least one selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment.

The content rate of the colorant (A) is preferably 0.1 to 60% by mass, more preferably 0.5 to 55% by mass, and still more preferably 1 to 50% by mass relative to the total amount of the solid content.

The content of the compound (1) is preferably at least 50% by mass, more preferably at least 80% by mass, and still more preferably at least 90% by mass in the total amount of the colorant (A).

In addition, the "total amount of solid content" in this specification means the amount excluding the content of a solvent from the total amount of a colored resin composition. The total amount of the solid content and the content of each component relative thereto can be measured, for example, by well-known analytical means such as liquid chromatography or gas chromatography.

The colored resin composition of the present invention may contain a polymerizable compound and/or a polymerization initiator. Hereinafter, the colored resin composition containing the polymerizable compound and the polymerization initiator may be referred to as "colored curable resin composition".

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by the active radical and/or acid generated by the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, etc. are mentioned, preferably For (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol tetra(meth)acrylate, di(meth)acrylate, Neopentaerythritol penta(meth)acrylate, dipivalerythritol hexa(meth)acrylate, etc.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2900 or less, more preferably 250 or more and 1500 or less.

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass relative to the total amount of solid content, Still more preferably, it is 17 to 55 mass %.

<Polymerization initiator (D)>

、2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑等。 The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. under the action of light and heat, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N- Benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl) -3-Cyclopentylpropan-1-one-2-imine, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6- pepper base-1,3,5-tri

, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, etc. .

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

The colored resin composition of the present invention may contain a polymerization initiation aid.

<Polymerization Initiating Auxiliary (D1)>

The polymerization initiator (D1) is a compound or a sensitizer for promoting the polymerization of the polymerizable compound in which the polymerization is initiated by the polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiator (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamine) base) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc.

When these polymerization initiators (D1) are used, their content is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with a further high sensitivity, and the productivity of the color filter tends to be improved.

The colored resin composition of the present invention preferably contains a solvent (E).

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. For example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecules), ether ester solvents (containing - COO- and -O- solvents), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule and no -O-, -CO- and -COO- solvent), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc.

Examples of the solvent (E) include ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, and acetoacetic acid. Ester solvents such as methyl ester, cyclohexanol acetate and γ-butyrolactone (solvents containing -COO- but not -O- in the molecule); ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and other ether solvents (containing -O- in the molecule and not containing -COO- solvent); methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ester ether acetate, diethylene glycol monoethyl ether acetate and other ether ester solvents (solvents containing -COO- and -O- in the molecule); 4-hydroxy-4-methyl-2-pentanone, Ketone solvents such as heptanone, 4-methyl-2-pentanone, and cyclohexanone (solvents containing -CO- and no -COO- in the molecule); alcohol solvents such as butanol, cyclohexanol, and propylene glycol (in the molecule). Solvents containing OH and not containing -O-, -CO- and -COO-); N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, etc. amide solvent.

As the solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferable.

When the solvent (E) is contained, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass with respect to the total amount of the colored resin composition of the present invention . In other words, the total amount of the solid content of the colored resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes favorable, and the color density does not become insufficient when the color filter is formed, so that the display characteristics tend to become favorable.

<Other ingredients>

The colored resin composition of the present invention may contain additives known in the technical field, such as leveling agents, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

<Manufacturing method of colored resin composition>

The colored resin composition of the present invention can be prepared by mixing a colorant (A), a resin (B), and optionally a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and other components used as needed. preparation.

<Manufacturing method of color filter>

As a method of producing a colored pattern from the colored resin composition of the present invention, a photolithography method, an inkjet method, a printing method, and the like can be mentioned. Among them, photolithography is preferred.

By including the compound of the present invention as a colorant in the colored resin composition, a color filter having particularly excellent light resistance can be produced. This color filter can be used as a color filter used in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[Example]

The following examples are given to illustrate the present invention in more detail. Of course, the present invention is not limited to the following examples, and can be appropriately modified and implemented within the scope that can be adapted to the gist of the preceding/after-mentioned. within the technical scope of the present invention.

In the following, unless otherwise specified, "part" means "mass part" and "%" means "mass %".

Example 1

6.7 parts of the compound represented by the formula (1x-1) and 5.0 parts of N-methyl-p-anisidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 30 parts of N-methyl-2-pyrrolidone, under 60 It was stirred at °C for 5 hours. After cooling the said reaction liquid to room temperature, 100 parts of water were added, and it stirred for 1 hour. The precipitated crystals were subjected to suction filtration, washed three times with 100 parts of water, and the crystals were dried under reduced pressure to obtain 9.8 parts of the compound represented by the formula (I-2).

Example 2

50.0 parts of the compound represented by the formula (1x-1) and 350 parts of isopropanol were mixed at room temperature, and 18.1 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the mixture at a temperature not exceeding 20° C. , and stirred at 20 °C for 3 hours. The reaction solution was put into 2100 parts of 10% hydrochloric acid. The obtained precipitate was obtained as a residue of suction filtration, washed with 373 parts of ion-exchanged water, and dried to obtain 23.6 parts of the compound represented by the formula (1y-1).

Next, 6.6 parts of the compound represented by formula (1y-1), 5.0 parts of 4-isopropoxyaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10.4 parts of potassium carbonate were added to N-methyl-2-pyrrolidone In 30 parts, it stirred at 80 degreeC for 5 hours. After cooling the said reaction liquid to room temperature, 100 parts of water were added, and it stirred for 1 hour. The precipitated crystals were suction filtered, washed three times with 100 parts of water, and the crystals were dried under reduced pressure to obtain 7.0 parts of the compound represented by the formula (I-114).

Further, 3.2 parts of the compound represented by the formula (I-114), 2.2 parts of 1-bromopropane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.5 parts of potassium carbonate were added to 30 parts of N-methyl-2-pyrrolidone, It was stirred at 80°C for 4 hours. After cooling the said reaction liquid to room temperature, 100 parts of water were added, and it stirred for 1 hour. The precipitated crystals were suction-filtered, washed three times with 100 parts of water, and the crystals were dried under reduced pressure to obtain 3.0 parts of the compound represented by the formula (I-138).

Synthesis Example 1

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was introduced at 0.02 L/min to create a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was placed, and heated to 70°C while stirring. . Next, 60 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) were added to Molar ratio 50:50 mixture) 440 parts were dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was dropped into a flask kept at 70°C over 4 hours using a dropping funnel.

On the other hand, 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl ether acetate 225 over 4 hours using a separate dropping funnel The resulting solution was dropped into the flask. After completion of the dropwise addition of the solution of the polymerization initiator, the solution was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a weight-average molecular weight (Mw) of 9.1×10 ³ , a molecular weight distribution of 2.16, and a solid content of 34.8. %, a resin B1 solution with an acid value of 81 mg-KOH/g in terms of solid content. Resin B1 has the structural unit shown below.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example was performed under the following conditions using the GPC method.

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Detector: Standard material for RI calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw/Mn) of the weight average molecular weight in terms of polystyrene obtained above and the number average molecular weight (Mw/Mn) was used as the molecular weight distribution.

Examples 3, 4 and Comparative Example 1

(Preparation of Colored Resin Composition)

Each component was mixed in the following composition, and the colored resin composition was obtained.

In Table 10, each component represents the following compounds.

(A-1): compound represented by formula (I-2)

(A-2): Compound represented by formula (I-138)

(A-3): Compound represented by formula (1-x)

(B-1): Resin B1 (solid content conversion)

(C-1): Dipivalerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (IRGACURE (registered trademark) OXE 01; manufactured by BASF)

(E-1): N-methylpyrrolidone

(E-2): Propylene glycol monomethyl ether acetate

<Production of coloring pattern>

The colored resin composition was applied on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Corporation) by spin coating, and then prebaked at 100° C. for 3 minutes to obtain a colored composition layer. After standing to cool, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used to expose it to 150 mJ/cm ² in an atmospheric environment. The exposure amount (365nm reference|standard) performed light irradiation. As a photomask, a photomask formed with a 100 μm line and space pattern was used. The light-irradiated coloring composition layer was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, washed with water, and then carried out in an oven at 230°C After 20 minutes of baking, a colored pattern was obtained.

<Lightfastness Evaluation>

An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by HOYA; cut off light of 380 nm or less) was placed on the colored patterns obtained in Examples 3, 4 and Comparative Example 1, and a light resistance tester (SUNTEST CPS+: Toyo Seiki) was used. Company) was irradiated with xenon light for 24 hours.

The chromaticity of the colored pattern after irradiation was measured, and the color difference before and after irradiation was obtained. The results are shown in Table 11.

[Industrial Availability]

By including the compound of the present invention as a colorant, a color filter having particularly excellent light resistance can be produced. This color filter can be used as a color filter used in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

Claims (4)

A colored resin composition comprising a compound represented by formula (1) and a resin:

In the formula (1), R ¹ represents a group represented by the formula (1x) as a substituent, and R ² to R ⁴ independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or R ¹ and R ³ represents a group represented by the formula (1x) as a substituent, and R ² and R ⁴ independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ¹ and R ² together may form a nitrogen atom-containing group. Ring, R ³ and R ⁴ together can form a ring containing a nitrogen atom, R ⁶ and R ⁷ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms

In formula (1x), R ⁸ represents an alkyl group having 1 to 8 carbon atoms, and * represents a bond terminal to a nitrogen atom. The colored resin composition according to claim 1, wherein R ⁸ is methyl, ethyl, n-propyl, isopropyl, or butyl. A color filter is formed of the colored resin composition described in claim 1 of the scope of application. A display device includes the color filter described in claim 3 of the patent application scope.