KR20180051395A - A compound, a colored photo resist composition, a color filter and a display device using the same - Google Patents

Abstract

A color filter formed with a conventional known colored resin composition may not sufficiently satisfy the light resistance. The present invention relates to a compound, a colored resin composition comprising the compound, a color filter formed with the colored resin composition, and a display device comprising the color filter. The compound of the present invention is represented by chemical formula (1).

Description

TECHNICAL FIELD [0001] The present invention relates to a color filter, and more particularly, to a color filter, a color filter, and a color filter.

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

BACKGROUND ART [0002] Colored resin compositions are used in the production of color filters used in display devices such as liquid crystal displays, electroluminescence displays, 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.

(Formula 1)

Japanese Laid-Open Patent Publication No. 2013-50693

The color filter formed of the colored resin composition containing the above-mentioned conventionally known compound may not be able to sufficiently satisfy the light resistance.

That is, the present invention includes the following inventions.

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

(Formula 1)

Wherein R ¹ to R ⁴ independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and at least 1 Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkyloxy group as a substituent and -CH ₂ - included in the saturated hydrocarbon group may be substituted with -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 together may form a ring containing a nitrogen atom.

And R ⁵ to R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[2] The organic electroluminescent device described in [1] or [2], wherein R ¹ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms and having an alkyloxy group as a substituent and R ² to R ⁴ independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms, , A hydrogen atom,

R ¹ and R ³ represent an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkyloxy group 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 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 alkyloxy group is a group represented by formula (1x)

(2)

In the general formula (2), R ⁸ represents an alkyl group having 1 to 8 carbon atoms. * Represents the bond with the nitrogen atom.]

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

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

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

[7] A display device comprising the color filter according to [6].

By including the compound of the present invention as a coloring agent in the colored resin composition, a color filter excellent in light resistance can be formed.

The compound of the present invention is represented by the formula (1) of the formula (1). Hereinafter, the compound represented by the formula (1) in the formula (1) may be referred to as " compound (1) ". The compound of the present invention also includes tautomers thereof and salts thereof. Each of the components and functional groups exemplified below can be used alone or in combination.

(Formula 1)

Wherein R ¹ to R ⁴ independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and at least one Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkyloxy group as a substituent and -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ⁵ -. R ¹ and R ² may form a ring containing a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together.

And R ⁵ to R ⁷ independently 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 toluyl group, a xylyl group, a mesyl group, a propylphenyl group and a butylphenyl group.

The alkyloxy 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.

The substituent groups that can also take the art aromatic hydrocarbon, halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8 , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , or -SO ₂ NR ⁹ R ¹⁰ , and the substituent thereof preferably substitutes the hydrogen atom contained in the aromatic hydrocarbon group. Among these, as the _{^{substituent, -OR 8, -SO 3 -,}} -SO 3 H, -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are _{^{preferred, -OR 8, -SO 3 - Z}} +, - SO ₂ NR ⁹ R ¹⁰ is more preferred. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ⁺ N (R ¹¹ ) ₄ .

However, Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ^{11 s} 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 - included in the saturated hydrocarbon group is -O-, -CO-, -NH - or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

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 the saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ⁸ to R ¹¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, a pentyl group, A straight chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, a 2-ethylhexyl group, etc., Branched chain alkyl group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

The hydrogen atom contained in the saturated hydrocarbon group in R ¹ to R ⁴ may be substituted with, for example, an aromatic hydrocarbon group or a halogen atom having 6 to 10 carbon atoms as a substituent. R may, and substituting the hydrogen atoms of the ¹ ~ R ⁴ saturated hydrocarbon groups as good an aromatic hydrocarbon group of 6 to 10 carbon atoms, R s ¹ ~ R ⁴ having 6 to 10 aromatic hydrocarbon group, the same group a group exemplified as the in .

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 the following. In the formula, * denotes a combined hand.

Examples of-OR ⁸ include methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, And an alkyloxy group such as an isocyanoyloxy group and an isocyanoyloxy group.

Examples of -CO ₂ R ⁸ include alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group and the like .

Examples of -SR ⁸ include alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and icosylsulfanyl group.

Examples of -SO ₂ R ⁸ include an alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include alkyloxys such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and icosyloxysulfonyl group, And the like.

Examples of -SO ₂ NR ⁹ R ^10, for example, sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) Sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl N-1 substitution, such as a sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

As _{^{R 5, -CO 2 H, -CO}} 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO ₂ NHR ⁹ are preferred, and -SO ^{_{3 -, -SO 3 - Z +}} , more preferably -SO ₃ H or -SO ₂ NHR ⁹ a.

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

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

Z ⁺ is _{^{a, + N (R 11) 4}} , Na + or K ^+, preferably N ⁺ (R ¹¹⁾ _4.

As the ⁺ N (R ¹¹ ) ₄ , it is preferable that at least two of the four R ^{11 s} are saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R < ¹¹ > s is preferably 20 to 80, more preferably 20 to 60. [

In the compound (1), R ¹ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms and having an alkyloxy group as a substituent, and R ² to R ⁴ are each independently a substituted or unsubstituted saturated A hydrocarbon group or a hydrogen atom or R ¹ and R ³ represent an aromatic hydrocarbon group having 6 to 10 carbon atoms and an alkyloxy group as a substituent and R ² and R ⁴ independently represent a substituent A saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a hydrogen atom.

The aromatic hydrocarbon group having 6 to 10 carbon atoms and having an alkyloxy group is preferably a group represented by the formula (1x).

(2)

In the general formula (2), R ⁸ represents an alkyl group having 1 to 8 carbon atoms. * Represents the bond with the nitrogen atom.]

As the alkyl group having 1 to 8 carbon atoms represented by R ^8, the above-mentioned R, and the carbon number of ⁸ include 1-8 alkyl groups, methyl group, ethyl group, n- propyl, isopropyl or butyl group is preferable, and methyl or isopropyl And a propyl group is more preferable.

As the compound (1), a compound represented by the formula (2) of the formula (3) (hereinafter sometimes referred to as a "compound (2)") is preferable. The compound (2) may be a tautomer thereof.

(Formula 3)

Wherein R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and at least one of R ²¹ to R ²⁴ represents an alkyl group having 6 to 20 carbon atoms, 10 < / RTI > aromatic hydrocarbon group. R ²¹ and R ²² may form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom.

And 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 described above as the aromatic hydrocarbon group of R ¹ to R ⁴ . The art of hydrogen atoms included aromatic hydrocarbon groups, -OR ^8, -SO ₃ ^- may be substituted with Z ^1+, -SO ₃ R ^26, or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

Examples of the alkyloxy group include the same groups as -OR ⁸ exemplified as the substituent of the aromatic hydrocarbon group represented by R ¹ , and a methoxy group, ethoxy group, n-propoxy group, isopropoxy group or butoxy group is preferable , A methoxy group or an isopropoxy group is more preferable.

The ring containing a nitrogen atom formed together with R ²¹ and R ²² and the ring containing a nitrogen atom formed by R ²³ and R ²⁴ may be the same as the ring formed by R ¹ and R ² together . Of these, aliphatic heterocyclic rings are preferred. Examples of the aliphatic heterocycle include the following. In the formula, * denotes a combined hand.

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

When R ²¹ to R ²⁴ are-R ²⁶ , -R ²⁶ is preferably independently of each other a methyl group or an ethyl group. Further, as R ²⁶ in -SO ₃ R ^26, and -SO ₂ NHR ^26, 3 to 20 carbon atoms in branched-chain alkyl group is preferred, and, and is a branched chain alkyl group having a carbon number of 6-12 and more preferably a 2-ethylhexyl group Is more preferable.

In the compound (2), R ²¹ represents an aromatic hydrocarbon group having an alkyloxy group and having 6 to 10 carbon atoms as a substituent, and R ²² to R ²⁴ independently represent a hydrogen atom or -R ²⁶ , Alternatively, it is preferable that R ²¹ and R ²³ represent an aromatic hydrocarbon group having 6 to 10 carbon atoms and an alkyloxy 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 and having an alkyloxy group, a group represented by the formula (1x) is preferable.

As the compound (1), a compound represented by the formula (3) of the formula (4) (hereinafter also referred to as "the compound (3)") is also preferable. The compound (3) may be a tautomer thereof.

(Formula 4)

In the general formula (4), 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 R ³¹ and R ³² is an aromatic hydrocarbon group having 6 to 10 carbon atoms Or a halogen atom, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkyloxy group having 1 to 3 carbon atoms, and -CH ₂ - included in the saturated hydrocarbon group of 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 alkylsulfanyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, or an alkyloxy group, and at least one of them is an alkyloxy group.

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

p and q independently represent an integer of 0 to 5; When p is 2 or more, plural R ^{33 s} may be the same or, when q is 2 or more, plural R ^{34 s} may be the same or different. However, the sum of p and q is 1 or more.

R ¹¹ has the same meaning as defined above.]

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms for R ³¹ and R ³² include groups having 1 to 10 carbon atoms among those represented by R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent include the same groups as those of R ¹ .

Examples of the alkyloxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group and a propoxy group.

R ³¹ and R ³² are preferably independently of each other a saturated hydrocarbon group having 1 to 3 carbon atoms.

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

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

Examples of the alkyloxy group for R ³³ and R ³⁴ include the same groups as those of -OR ⁸ exemplified as the substituent of the aromatic hydrocarbon group represented by R ^1. Examples of the alkyloxy group include methoxy, ethoxy, n-propoxy, Or a butoxy group is preferable, and a methoxy group or an isopropoxy group is more preferable.

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

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

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

The compound (3) is preferably a compound represented by the formula (3-1) of the formula (5).

(Formula 5)

Wherein R ³¹ and R ³² have the same meanings as defined 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 a group having 1 to 8 carbon atoms in R ⁸ described above, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a butyl group is preferable, Or an isopropyl group is more preferable.

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

(Formula 6)

(Table 1)

(Table 2)

(Table 3)

(Table 4)

(Table 5)

(Table 6)

(Table 7)

(Table 8)

(Table 9)

Wherein, H represents a hydrogen atom, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, iPr represents a 2-propyl group, Bu represents an n-butyl group, 2EH represents a 2-ethylhexyl group, (p8) each represent the following groups. In the formula, * denotes a combined hand.

(h1) to (h4) represent that R ^3a and R ^4a together form the following rings. In the formula, * denotes a combined hand.

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

The compound (1) can be produced by reacting a compound represented by the formula (1x), a compound represented by the formula (1z-1) and a compound represented by the formula (1z-2) in the presence or absence of an organic solvent Method. The reaction temperature is preferably from 30 to 180, more preferably from 50 to 110. [ The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

[Wherein R ¹ to R ⁷ are the same as defined above] in the formula (1x), the formula (1z-1), the formula (1z-2) and the formula (1)

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, nitrohydrocarbon solvents such as nitrobenzene, and methyl isobutyl ketone Amide solvents such as 1-methyl-2-pyrrolidone; and the like.

The 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 and 8 mol or less per mol of the compound represented by the formula (1x) Is 1 mol or more and 5 mol or less. The reaction may be carried out stepwise or simultaneously.

When the 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)"), the compound (1a) The resulting compound may be further reacted in the presence or absence of an organic solvent. The reaction temperature is preferably from 30 to 180, more preferably from 50 to 110. [ The reaction time is preferably 1 to 12 hours, more preferably 3 to 8 hours.

(Formula 7)

Wherein R ¹² represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

Examples of the organic solvent include the same solvents as those exemplified as the organic solvent for the reaction of the compound (1x) with the compounds (1z-1) and (1z-2).

When the compound represented by the formula (1a) and the compound represented by the formula (1z-3) are reacted, a basic substance such as sodium carbonate or potassium carbonate may be coexistent.

The method for obtaining the desired compound (1) 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 filtered. The temperature at which the reaction mixture and water are mixed is preferably 10 or more and 50 or less. Thereafter, stirring is preferably performed at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known technique such as recrystallization.

The colored resin composition of the present invention includes 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 further preferably 1 to 20 parts by mass with respect 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 at least one kind (a) (hereinafter referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride ) Is more preferable. The resin (B) may further contain a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter also referred to as "(b)") (Hereinafter sometimes referred to as " (c) ") which is copolymerizable with the monomer (c) (provided that (a) and (b) are different), and a structural unit derived from an ethylenically unsaturated bond Having at least one kind of structural unit selected from the group consisting of structural units having the above-mentioned structural units.

(a) include, for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono [2- (meth) Oxyethyl], and the like, and preferably acrylic acid, methacrylic acid, maleic anhydride.

(b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of oxirane rings, oxetane rings and tetrahydrofuran rings) and a monomer having a (meth) acryloyloxy group .

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, 3-ethyl (Meth) acryloyloxymethyl oxetane, tetrahydrofurfuryl (meth) acrylate and the like, and preferred examples thereof include glycidyl (meth) acrylate, 3,4-epoxy tricyclo [ 5.2.1.0 ^2,6 ] decyl (meth) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

(meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decan-8-yl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N- phenyl maleimide, N- cyclohexyl maleimide, N- benzyl maleimide and styrene , Vinyl toluene, and the like. Of these, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are preferable.

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

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 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, 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 still more preferably 70 to 135 mg-KOH / g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

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

≪ Colorant (A) >

The colored resin composition of the present invention may contain, as the colorant (A), the dye (A1) and the pigment (A2) 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, mordant dyes and the like. Examples of the dyes include compounds classified in the color index (published by The Society of Dyers and Colourists) as having a color other than pigment, and known dyes described in dyeing notes . Further, according to the chemical structure, it is possible to use azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, Styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred. The dyes described in JP-A-2015-28121, JP-A-2013-7032, JP-A-2013-144724 and JP-A-2013-53292 are also preferable.

The pigment (A2) is not particularly limited and a known pigment can be used. For example, the pigment classified in the color index (The Society of Dyers and Colourists) is classified as a pigment.

As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

And the like.

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 a blue pigment and a violet pigment.

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 yellow pigment, orange pigment and red pigment.

The content of the colorant (A) is preferably from 0.1 to 60 mass%, more preferably from 0.5 to 55 mass%, and still more preferably from 1 to 50 mass%, based on the total amount of the solid components.

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

Here, the "total amount of solid content" in the present specification means the amount excluding the content of the solvent from the total amount of the colored resin composition. The total amount of the solid content and the content of each component can be measured by a 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 comprising the polymerizable compound and the polymerization initiator may be referred to as a " colored curable resin composition ".

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of being polymerized by an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenic unsaturated bond, Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) , Dipentaerythritol hexa (meth) acrylate, and the like.

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

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, By mass to 17% by mass to 55% by mass.

≪ Polymerization initiator (D) >

The polymerization initiator (D) is not particularly limited as far as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexyl Phenyl ketone, 2,4-bis (trichloromethyl) -6-piperonyl 1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis -Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.

When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) 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) Is 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity of the color filter tends to be shortened and the exposure time is shortened.

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

≪ Polymerization initiator (D1) >

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

Examples of the polymerization initiator (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly referred to as Mihiraazuketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl thioxanthone, N-phenylglycine, and the like.

When these polymerization initiator (D1) is used, its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Mass part. When the amount of the polymerization initiator (D1) is within this range, it is possible to form a colored pattern with higher 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 commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like.

Examples of the solvent (E) include ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone An ester solvent (a solvent containing -COO- in the molecule and not containing -O-);

Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether, A solvent not including -COO-);

Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and diethylene glycol monoethyl ether acetate A solvent containing -COO- and -O-);

Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone (containing -CO- in the molecule, solvent);

Alcohol solvents such as butanol, cyclohexanol and propylene glycol (solvents containing OH in the molecule and not including -O-, -CO- and -COO-);

Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

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 mass%, and more preferably 75 to 92 mass%, based on the total amount of the colored resin composition of the present invention. In other words, the total amount of solids in the colored resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% 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 color density tends not to be insufficient when the color filter is further formed.

<Other components>

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

&Lt; Production method of colored resin composition &gt;

The colored resin composition of the present invention is prepared by mixing a colorant (A), a resin (B), and a polymerizable compound (C), a polymerization initiator (D), a solvent (E) .

<Manufacturing Method of Color Filter>

Examples of a method for producing a colored pattern from the colored resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Among them, the photolithography method is preferable.

By including the compound of the present invention as a coloring agent in the colored resin composition, a color filter having excellent light resistance can be produced. Such a color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, but the present invention is not limited to the following Examples. Of course, all of which are within the technical scope of the present invention.

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

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 Kasei Kogyo Co., Ltd.) were added to 30 parts of N-methyl-2-pyrrolidone, Lt; / RTI &gt; After the reaction solution was cooled to room temperature, 100 parts of water was added and the mixture was stirred for 1 hour. The precipitated crystals were suction filtered and washed three times with 100 parts of water, and the crystals were dried under reduced pressure to obtain 9.8 parts of a compound represented by the formula (I-2).

(Formula 8)

(Formula 9)

Example 2

50.0 parts of the compound represented by the formula (1x-1) and 350 parts of isopropyl alcohol were mixed at room temperature and 18.1 parts of diethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise to the mixture at a temperature not exceeding 20 Lt; / RTI &gt; for 3 hours. The reaction solution was poured into 2100 parts of 10% hydrochloric acid. The obtained precipitate was collected as a residue of suction filtration and washed and dried in 373 parts of ion-exchanged water to obtain 23.6 parts of a compound represented by the formula (1y-1).

(Formula 10)

Subsequently, 6.6 parts of the compound represented by the formula (1y-1), 5.0 parts of 4-isopropoxyaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 10.4 parts of potassium carbonate were added to 30 parts of N-methyl-2-pyrrolidone , And the mixture was stirred at 80 DEG C for 5 hours. After the reaction solution was cooled to room temperature, 100 parts of water was added and the mixture was stirred for 1 hour. The precipitated crystals were collected by suction filtration and washed three times with 100 parts of water, and the crystals were dried under reduced pressure to obtain 7.0 parts of a compound represented by the formula (I-114).

(Formula 11)

3.2 parts of the compound represented by the formula (I-114), 2.2 parts of 1-bromopropane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 2.5 parts of potassium carbonate were added to 30 parts of N-methyl- The mixture was stirred for 4 hours. After the reaction solution was cooled to room temperature, 100 parts of water was added and the mixture was stirred for 1 hour. The precipitated crystals were suction filtered and washed with 100 parts of water three times, and the crystals were dried under reduced pressure to obtain 3.0 parts of a compound represented by the formula (I-138).

(12)

Synthesis Example 1

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

(13)

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 4 hours using another dropping funnel . After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70 ° C. for 4 hours and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 × 10 ³ , the molecular weight distribution was 2.16, the solid content was 34.8% To obtain a resin B1 solution having an acid value of 81 mg-KOH / g. Resin B1 has the following structural unit.

(14)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in Synthesis Example were measured by the GPC method under the following conditions.

K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL / min

Detector; Reference material for RI calibration; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500 and A-500 (manufactured by Tosoh Corporation)

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

Examples 3 and 4 and Comparative Example 1

(Preparation of colored resin composition)

Each component was mixed with the following composition to obtain a colored resin composition.

(Table 1)

In Table 10, each component represents the following compound.

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

(A-2): A compound represented by the formula (I-138)

(A-3): A compound represented by the formula (1-x)

(Formula 15)

(B-1): Resin B1 (in terms of solid content)

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

(Irgacure (registered trademark) OXE 01, manufactured by BASF) was added to the mixture of (D-1): N-benzoyloxy-1- (4-phenylsulfanylphenyl)

(E-1): N-methylpyrrolidone

(E-2): Propylene glycol monomethyl ether acetate

&Lt; Fabrication of coloring pattern &

The colored resin composition was coated on a glass substrate (Eagle 2000; Corning) having a 5 cm edge by spin coating, and then prebaked at 100 for 3 minutes to obtain a coloring composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 mu m and the exposure amount (365 nm) was measured using an exposure machine (TME-150RSK; ). As the photomask, a 100 μm line and space pattern was formed. After the light irradiation, the coloring composition layer was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 24 to 60 seconds, washed with water and then post baked in an oven at 230 for 20 minutes, A colored pattern was obtained.

&Lt; Evaluation of light resistance &

An ultraviolet cut filter (COLORED OPTICAL GLASS L38, made by Hoya Co., Ltd., cut off light of 380 nm or less) was placed on the coloring patterns obtained in Examples 3 and 4 and Comparative Example 1, and a light resistance tester (SUNTEST CPS + Xenon lamp light was irradiated for 24 hours.

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

(Table 11)

By including the compound of the present invention as a coloring agent, a color filter excellent in light resistance can be produced. Such a color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

Claims (7)

A compound represented by the formula (1).
(Formula 1)

[Chemical Formula 1]
R ¹ to R ⁴ independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and at least one of R ¹ to R ⁴ is an alkyl -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ⁵ -;
R ¹ and R ² may together form a ring containing a nitrogen atom;
R ³ and R ⁴ may together form a ring containing a nitrogen atom;
And R ⁵ to R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The method according to claim 1,
Wherein R ¹ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms and an alkyloxy group 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 a hydrogen atom Or, alternatively,
R ¹ and R ³ represent an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkyloxy group 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, , A hydrogen atom.
3. The method according to claim 1 or 2,
Wherein the aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkyloxy group is a group represented by the formula (2).
(2)

In Formula 2,
R ⁸ represents an alkyl group having 1 to 8 carbon atoms;
* Represents the bond with the nitrogen atom.]
3. The method according to claim 1 or 2,
Wherein R ⁸ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a butyl group.
A colored resin composition comprising the compound according to any one of claims 1 to 3 and a resin.
A color filter formed from the colored resin composition according to claim 5.
A display device comprising the color filter according to claim 6.