KR102328365B1 - A compound, a colored photo resist composition, a color filter and a display device using the same - Google Patents

Abstract

The color filter formed from the conventionally known colored resin composition may not fully satisfy light resistance. 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, wherein the compound of the present invention is represented by Formula (1).

Description

A compound, a colored resin composition including the compound, a color filter formed of the colored resin composition, and a display device including the color filter {A compound, a colored photo resist composition, a color filter and a display device using the same}

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.

A colored resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display. As such a colored resin composition, the colored resin composition containing the compound represented by a following formula as a coloring agent is known.

(Formula 1)

Japanese Laid-Open Patent Publication No. 2013-50693

The color filter formed from the conventionally known colored resin composition containing said compound may not fully satisfy light resistance.

That is, the present invention includes the following inventions.

[1] The compound represented by Formula (1) of Formula 1.

(Formula 1)

[In Formula 1, R ¹ to ^{R 4} represent, independently of each other, 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 Each represents a C6-C10 aromatic hydrocarbon group having an alkyloxy group as a substituent, and -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, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

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

[2] R ¹ represents an aromatic hydrocarbon group having 6 to 10 carbon atoms having an alkyloxy group as a substituent, and R ² to R ⁴ are, independently of each other, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or , represents a hydrogen atom, or,

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 are, independently of each other, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or , the compound according to [1], wherein a hydrogen atom is represented.

[3] The compound according to [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 (1x) of the general formula (2).

(Formula 2)

[In the formula (2), R ⁸ represents an alkyl group having 1 to 8 carbon atoms. * indicates a bond with a 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 the compound and resin according to any one of [1] to [4].

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

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

When a colored resin composition contains the compound of this invention as a coloring agent, the color filter excellent in light resistance can be formed.

The compound of this invention is represented by Formula (1) of Formula (1). Hereinafter, the compound represented by Formula (1) of Formula 1 may be called "compound (1)." The compounds of the present invention also include tautomers and salts thereof. In addition, each component and functional group illustrated below can be used individually or in combination, respectively.

(Formula 1)

[In Formula 1, R ¹ to R ⁴ represent, independently of each other, a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, or an aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent, and at least one represents a C6-C10 aromatic hydrocarbon group having an alkyloxy group as a substituent, and -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, and R ³ and R ⁴ together may form a ring containing a nitrogen atom.

R ⁵ to R ⁷ each 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 for R ¹ to R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl 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 there may be mentioned _{^{2 R 8, -SO 3 R 8}} , or -SO ₂ NR ⁹ R ^10, the substituent thereof is preferably a hydrogen atom and a substituted aromatic hydrocarbon groups are included. 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 preferable. -SO ₃ in this case ^- as Z ^+, a _{^{-SO 3 + N (R 11)}} 4 are preferred.

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

R ⁹ and R ¹⁰ each 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 is -O-, -CO-, -NH It may be substituted with - 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, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, Linear alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, etc. Branched alkyl group; A C3-C20 alicyclic saturated hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, is mentioned.

Hydrogen atoms contained art groups saturated hydrocarbon in R ¹ ~ R ⁴ it is, for example, may be substituted with a carbon number of 6 to 10 aromatic hydrocarbon group or a halogen atom 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 can

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

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, * represents a bond.

-OR ^{8 is} , for example, a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexylox group Alkyloxy groups, such as time and an isosyloxy group, etc. are mentioned.

As -CO ₂ R ⁸ , for example, alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group, etc. can be heard

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

Examples of -SO ₂ R ^8, for example, there may be mentioned an alkylsulfonyl group such as a methyl sulfonyl group, ethyl sulfonyl, butyl sulfonyl group, hexyl sulfonyl group, sulfonyl group and decyl Ikoma room sulfonyl group.

As -SO ₃ R ⁸ , for example, an alkyloxysulfonyl group such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group A phonyl group etc. are mentioned.

-SO ₂ NR ⁹ R ^{10 is} , for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulf Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1, 2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-( 3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamo Diyl, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethylhexyl)sulfamoyl group, and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group etc. are mentioned.

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 it is preferred, and -SO ^{_{3 -, -SO 3 - Z +}} , more preferably -SO ₃ H or -SO ₂ NHR ⁹ a.

As the carbon number of alkyl group R of 1 to 6 in the ⁵ ~ R ^7, may be mentioned any of the alkyl groups in the above, the group having 1 to 6 carbon atoms. 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 ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

Examples of the N ⁺ (R ¹¹⁾ _4, of the four R ^11, preferably at least two saturated hydrocarbon group having a carbon number of 5-20. Moreover, 20-80 are preferable and, as for total carbon number of four R<^{11>, 20-60 are more preferable.}

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

As a C6-C10 aromatic hydrocarbon group which has the said alkyloxy group, the group represented by Formula (1x) is preferable.

(Formula 2)

[In the formula (2), R ⁸ represents an alkyl group having 1 to 8 carbon atoms. * indicates a bond with a 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 A propyl group is more preferable.

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

(Formula 3)

[In Formula 3, R ²¹ to R ²⁴ represent, independently of each other, a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, at least one having an alkyloxy group as a substituent 6 to C 6 10 represents an aromatic hydrocarbon group. R ²¹ and R ²² may together form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may together form a ring containing a nitrogen atom.

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 for R ²¹ to R ²⁴ include the same groups as those mentioned as the aromatic hydrocarbon group for ^{R 1} to R ^{4 above.} 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 a 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.

Examples of ^{the ring containing a nitrogen atom that R 21} and R ²² form together and the ring containing a nitrogen atom that R ²³ and R ²⁴ form together include the same as the ring formed by ^{R 1} and R ^{2 together.} . Especially, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following. In the formula, * represents a bond.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms for R ²⁶ include the same groups as ^{the saturated hydrocarbon group for R 8} to R ^{11 .}

When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is each independently preferably 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 6 to 10 carbon atoms having an alkyloxy group as a substituent, and R ²² to R ²⁴ each 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 having an alkyloxy group as a substituent, and R ²² and R ²⁴ each independently represent a hydrogen atom or —R ^{26 .}

As a C6-C10 aromatic hydrocarbon group which has the said alkyloxy group, the group represented by Formula (1x) is preferable.

Further, as the compound (1), a compound represented by the formula (3) of the general formula (4) (hereinafter sometimes referred to as “compound (3)”) is also preferable. Compound (3) may be a tautomer thereof.

(Formula 4)

[In the formula (4), R ³¹ and R ³² each 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 it may be substituted with 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, _{-CH 2} - contained in the saturated hydrocarbon group of ^{R 31} and R ³² is - It may be substituted by O-, -CO-, or -NR ^{11 -.}

R ³³ and R ³⁴ each 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 represents an alkyloxy group.

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

p and q each independently represent the integer of 0-5. When p is 2 or more, a plurality of R ³³ may be the same, 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 group having 1 to 10 carbon atoms for R ³¹ and R ³² include a group having 1 to 10 carbon atoms among those ^{for R 8 .}

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that may be included as the substituent include the same groups as those ^{for R 1 .}

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

R ³¹ and R ³² are each independently preferably 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 in 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 in 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 for -OR 8} exemplified as a substituent of the aromatic hydrocarbon group represented by ^{R 1} , a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. A group 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.

The integer of 0-2 is preferable and, as for p and q, 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.

It is preferable that compound (3) is a compound represented by Formula (3-1) of Formula (5).

(Formula 5)

[In Formula 5, R ³¹ and R ³² are the same as above. R ³⁸ and R ³⁹ each 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 groups having 1 to 8 carbon atoms among R 8} described above, and a methyl group, ethyl group, n-propyl group, isopropyl group or butyl group is preferable, and a methyl group is preferable. Or an isopropyl group is more preferable.

As compound (1), compounds (I-1) - (I-504) represented by Formula (I) of Formula (6) are mentioned, for example.

(Formula 6)

(Table 1)

(Table 2)

(Table 3)

(Table 4)

(Table 5)

(Table 6)

(Table 7)

(Table 8)

(Table 9)

However, H represents a hydrogen atom, Me represents a methyl group, Et represents an ethyl group, Pr represents a n-propyl group, iPr represents a 2-propyl group, Bu represents an n-butyl group, 2EH represents a 2-ethylhexyl group, (p1)- (p8) represents the following groups, respectively. In the formula, * represents a bond.

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

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

As a method for producing compound (1), a compound represented by formula (1x), a compound represented by formula (1z-1), and a compound represented by formula (1z-2) are reacted in the presence or absence of an organic solvent. method can be found. It is preferable that it is 30-180, and, as for reaction temperature, it is more preferable that it is 50-110. It is preferable that it is 1 to 12 hours, and, as for reaction time, it is more preferable that it is 3 to 8 hours.

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

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; methyl isobutyl ketone, etc. ketone solvents; 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) to be used is preferably 1 mol or more and 8 mol or less, respectively, with respect to 1 mol of the compound represented by the formula (1x), more preferably is 1 mole or more and 5 moles or less. You may make it react stepwise, respectively, and you may make it react 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) and formula (1z-3) You may make the appearing compound further react in presence or absence of an organic solvent. It is preferable that it is 30-180, and, as for reaction temperature, it is more preferable that it is 50-110. It is preferable that it is 1 to 12 hours, and, as for reaction time, it is more preferable that it is 3 to 8 hours.

(Formula 7)

[In the formula (7), 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 organic solvents for reacting compound (1x) with compounds (1z-1) and (1z-2).

When making compound (1a) and the compound represented by Formula (1z-3) react, you may make basic substances, such as sodium carbonate and potassium carbonate, coexist.

The method for obtaining 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 a reaction mixture and water becomes like this. Preferably it is 10 or more and 50 or less. Moreover, after this, it is preferable to stir at the same temperature for about 0.5 to 2 hours. It is preferable to wash the crystal|crystallization obtained by filtration with water etc., and to dry then. Moreover, you may further refine|purify by well-known methods, such as recrystallization, as needed.

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

It is preferable that content of a compound (1) is 0.1-100 mass parts with respect to 100 mass parts of resin, It is more preferable that it is 1-50 mass parts, It is more preferable that it is 1-20 mass parts.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is an alkali-soluble resin, At least 1 type (a) selected from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter referred to as "(a)" may A resin having a structural unit derived from ) is more preferable. The resin (B) further has a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, a structural unit derived from a monomer (b) (hereinafter sometimes referred to as “(b)”), (a) Structural unit derived from monomer (c) copolymerizable with and (however, (a) and (b) are different.) (hereinafter sometimes referred to as "(c)"), and an ethylenically unsaturated bond in the side chain It is preferable to have at least 1 sort(s) of structural unit selected from the group which consists of structural units which have.

Specifically as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-(meth)acryloyl oxyethyl], etc. are mentioned, Preferably, they are acrylic acid, methacrylic acid, and maleic anhydride.

(b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and a (meth)acryloyloxy group is preferable

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

As (b), for example, glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, 3-ethyl -3-(meth)acryloyloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate, etc. are mentioned, Preferably, glycidyl (meth)acrylate, 3,4-epoxy tricyclo [ 5.2.1.0 ^2,6 ] It is decyl (meth)acrylate and 3-ethyl-3- (meth)acryloyloxymethyloxetane.

As (c), for example, methyl (meth) acrylate, butyl (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, styrene , vinyltoluene, etc. are mentioned, Preferably, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc. are preferable.

The resin having a structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding (b) to the copolymer of (a) and (c), or adding (a) to the copolymer of (b) and (c). It can be manufactured by The resin may be a resin in which (a) is added to the copolymer of (b) and (c) and further reacted with a carboxylic acid anhydride.

The weight average molecular weight of resin (B) in terms of polystyrene becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this in conversion of solid content, Preferably it is 50-170 mg-KOH/g, More preferably, it is 60-150, More preferably, it is 70-135 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required in order to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ the content rate of resin (B) ] with respect to the total amount of solid content, Preferably it is 7-65 mass %, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %.

<Colorant (A)>

The colored resin composition of this invention may contain the dye (A1) and the pigment (A2) other than the compound (1) as a coloring agent (A).

The dye (A1) is not specifically limited, A well-known dye can be used, For example, a solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned. As the dye, for example, a compound classified as having a color other than a pigment in the color index (published by The Society of Dyers and Colorists), and a known dye described in a dyeing note (color dyeing yarn) can be mentioned. . 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, azomethine dyes, scaryllium dyes, azo dyes Creidine dye, styryl dye, coumarin dye, quinoline dye, nitro dye, etc. are mentioned. Among these, organic solvent-soluble dyes are preferable. Moreover, as dye, the dye of 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 by the color index (The Society of Dyers and Colorists publication) is mentioned.

As a pigment, it is CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, for example. , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments;

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, 265 ;

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 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 this invention is a blue colored resin composition, as for a pigment, at least 1 sort(s) chosen from the group which consists of a blue pigment and a violet color pigment is preferable.

When the colored resin composition of this invention is a red colored resin composition, as for a pigment, at least 1 sort(s) chosen from the group which consists of a yellow pigment, an orange pigment, and a red pigment is preferable.

To [ the content rate of a coloring agent (A) ] with respect to the total amount of solid content, Preferably it is 0.1-60 mass %, More preferably, it is 0.5-55 mass %, More preferably, it is 1-50 mass %.

It is preferable that it is 50 mass % or more in the total amount of a coloring agent (A), as for the content rate of a compound (1), it is more preferable that it is 80 mass % or more, It is still more preferable that it is 90 mass % or more.

Here, the "total amount of solid content" in this specification means the quantity which removed content of the solvent from the total amount of a colored resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

The colored resin composition of this invention may contain the polymeric compound and/or the polymerization initiator. Hereinafter, the colored resin composition containing a polymeric compound and a polymerization initiator may be called "colored curable resin composition."

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, preferably It is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , dipentaerythritol hexa(meth)acrylate, and the like.

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, they are 250 or more and 1,500 or less.

When a polymeric compound (C) is included, it is preferable that the content rate of a polymeric compound (C) is 7-65 mass % with respect to the total amount of solid content, More preferably, it is 13-60 mass %, More preferably Usually, it is 17-55 mass %.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used. As a polymerization initiator which generate|occur|produces an active radical, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulf), for example. Panylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, 2-methyl-2-morph Polyno-1-(4-methylsulfanylphenyl)propan-1-one, 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(2) -Chlorophenyl)-4,4', 5, 5'- tetraphenylbiimidazole, etc. are mentioned.

When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

The colored resin composition of this invention may contain the polymerization initiation adjuvant.

<Polymerization initiation aid (D1)>

A polymerization initiation adjuvant (D1) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator, or a sensitizer. When a polymerization initiation adjuvant (D1) is included, it is used in combination with a polymerization initiator (D) normally.

Examples of the polymerization initiation adjuvant (D1) include 4,4'-bis(dimethylamino)benzophenone (common name mihirazketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc. are mentioned.

When using these polymerization initiation adjuvant (D1), the content is with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. is the mass part. When the amount of the polymerization initiation auxiliary (D1) is within this range, a coloring pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

It is preferable that the colored resin composition of this invention contains a solvent (E).

<Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvent (solvent containing -COO- in a molecule|numerator and not containing -O-), ether solvent (solvent containing -O- in a molecule|numerator and not containing -COO-), ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule, - solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

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

Ether solvents such as 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 (in the molecule -O- A solvent that contains and does not contain -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 (in the molecule Solvent containing -COO- and -O-);

Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, and cyclohexanone (with -CO- in the molecule and not -COO- solvent);

Alcohol solvents, such as butanol, cyclohexanol, and propylene glycol (a solvent which contains OH in a molecule|numerator and does not contain -O-, -CO-, and -COO-);

and 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 a solvent (E) is included, with respect to the total amount of the colored resin composition of this invention, the content rate of a solvent (E) becomes like this. Preferably it is 70-95 mass %, More preferably, it is 75-92 mass %. In other words, the total amount of solid content of a colored resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is further formed, there exists a tendency for a display characteristic to become favorable.

<Other ingredients>

The coloring composition of this invention may contain well-known additives in this technical field, such as a leveling agent, a filler, another high molecular compound, an adhesion promoter, antioxidant, a light stabilizer, and a chain transfer agent, as needed.

<The manufacturing method of a colored resin composition>

The colored resin composition of the present invention may 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. can

<The manufacturing method of a color filter>

As a method of manufacturing a colored pattern from the colored resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable.

When a colored resin composition contains the compound of this invention as a coloring agent, especially the color filter excellent in light resistance can be produced. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples from the beginning, and is carried out with appropriate changes within a range that can be suitable for the purpose of the previous and later It is of course also possible, and they are all included in the technical scope of the present invention.

In addition, in the following, unless otherwise indicated, "part" means "mass part" and "%" means "mass %".

Example 1

6.7 parts of a compound represented by Formula (1x-1) and 5.0 parts of N-methyl-p-anisidine (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 30 parts of N-methyl-2-pyrrolidone, 60 to 5 hours stirred. After cooling said reaction liquid to room temperature, 100 parts of water was added, and it stirred for 1 hour. The precipitated crystals were suction filtered, washed 3 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 are mixed at room temperature, and 18.1 parts of diethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is added dropwise to the mixture at a temperature not exceeding 20, 20 was stirred for 3 hours. The reaction solution was poured into 2100 parts of 10% hydrochloric acid. The obtained precipitate was acquired as a residue of suction filtration, it wash-dried with 373 parts of ion-exchange water, and 23.6 parts of compounds represented by Formula (1y-1) were obtained.

(Formula 10)

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 are added to 30 parts of N-methyl-2-pyrrolidone, , and stirred at 80°C for 5 hours. After cooling said reaction liquid to room temperature, 100 parts of water was added, and it stirred for 1 hour. The precipitated crystals were suction filtered, washed 3 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).

(Formula 11)

Furthermore, 3.2 parts of compounds represented by Formula (I-114), 2.2 parts of 1-bromopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.5 parts of potassium carbonate are added to 30 parts of N-methyl-2-pyrrolidone, and 80 The mixture was stirred for 4 hours. After cooling said reaction liquid to room temperature, 100 parts of water was added, and it stirred for 1 hour. The precipitated crystals were suction filtered, washed 3 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).

(Formula 12)

Synthesis Example 1

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, 305 parts of propylene glycol monomethyl ether acetate was put, and it was heated to 70 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) is 50 : Mix at 50.) 440 parts were melt|dissolved in 140 parts of propylene glycol monomethyl ether acetate, the solution was prepared, and the said solution was dripped in the flask kept at 70 over 4 hours using the dropping funnel.

(Formula 13)

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

(Formula 14)

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

Apparatus; K2479 (manufactured by Shimadzu Corporation)

Column：SHIMADZU　Shim-pack　GPC-80M

Column temperature; 40

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 mL/min

Detector; Standard for RI Calibration　; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500 (made by Toso Corporation)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution.

Examples 3, 4 and Comparative Example 1

(Preparation of colored resin composition)

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

(Table 1)

In Table 10, each component shows the following compounds.

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

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

(A-3): The compound represented by Formula (1-x)

(Formula 15)

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

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

(D-1): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-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 a coloring pattern>

After apply|coating the colored resin composition by the spin coating method on the glass substrate (Eagle 2000; Corning company make) of 5 cm corner, it prebaked at 100 for 3 minutes, and obtained the coloring composition layer. After standing to cool, the interval between the substrate on which the coloring composition layer was formed and the quartz glass photomask was set to 100 µm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an atmospheric atmosphere, and an exposure amount of 150 mJ/cm 2 (based on 365 nm) ) was irradiated with light. As a photomask, the thing in which the 100 micrometers line-and-space pattern was formed was used. The coloring composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 24 to 60 seconds, and after washing with water, in an oven, post-baking at 230 for 20 minutes, A coloring pattern was obtained.

<Light fastness evaluation>

An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Corporation; cuts light of 380 nm or less) was placed on the colored pattern obtained in Examples 3 and 4 and Comparative Example 1, and a light resistance tester (SUNTEST CPS +: Toyosei Corporation) was placed. The product was irradiated with a xenon lamp light for 24 hours.

The chromaticity of the coloring pattern after irradiation was measured, and the color difference before and behind irradiation was calculated|required. A result is shown in Table 11.

(Table 11)

By including the compound of this invention as a coloring agent, the color filter excellent in especially light resistance can be produced. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Claims (7)

It contains a compound and a resin represented by Formula 1,
A colored resin composition for use in a color filter.
(Formula 1)

[In Formula 1,
R ¹ represents any one group selected from the group consisting of the following (p1) to (p8), and R ² to R ⁴ are, independently of each other, a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, Or, represents a hydrogen atom, or,
R ¹ and R ³ each independently represent any one group selected from the group consisting of the following (p1) to (p8), and R ² and R ⁴ are, independently of each other, having a substituent having 1 to A saturated hydrocarbon group of 20, or a hydrogen atom,
_{-CH 2} - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ^{5 -;}
R ³ and R ⁴ together may form a ring containing a nitrogen atom;
R ⁵ to R ⁷ represent, independently of each other, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
In the formula, * represents a bond.]

delete delete delete delete The color filter formed from the colored resin composition of Claim 1.
A display device comprising the color filter according to claim 6 .