KR20200106501A - Compound, colored resin composition, color filter and display device - Google Patents

Abstract

The present invention provides a compound and a colored resin composition capable of forming a color filter and display device excellent in heat resistance.

Description

Compound, colored resin composition, color filter and display device

The present invention relates to compounds.

A color filter used in a liquid crystal display device, an electroluminescent display device, a display device such as a plasma display, or a solid-state imaging device such as a CCD or a CMOS sensor is made of a colored resin composition. As a colorant used in such a colored resin composition, a compound represented by formula (X) is known.

However, a conventionally known color filter formed of a colored resin composition containing the above compound may not sufficiently satisfy heat resistance. Therefore, the present invention provides a compound capable of forming a color filter excellent in heat resistance.

The present invention includes the following inventions.

[1] A compound represented by a formula (IA), a formula (IB), or a formula (IC).

[In formula (IA),

Each of R ¹ to R ⁸ independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

R ^9A to R ^12A each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9A to R ^12A is a hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent to be.

QA ⁿ⁺ represents an n-valent metal ion.

n represents an integer of 2 or more.

bA represents the number of QA ⁿ⁺ .

When the total of negative charges included in R ¹ to R ⁸ and R ^9A to R ^12A is kA, aA is (n×bA)/kA.]

[In formula (IB),

R ¹ to R ⁸ represent the same meaning as above.

R ^9B to R ^12B each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9B to R ^12B is an aliphatic hydrocarbon having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent. It is.

QB ⁿ⁺ represents a hydrone or an n-valent metal ion.

n represents an integer of 2 or more.

bB represents the number of QB ⁿ⁺ .

When the sum of -SO ₃ ^- contained in R ¹ to R ⁸ and R ^9B to R ^12B is kB, aB is (n×bB)/kB.]

In [Formula IC],

R ¹ to R ⁸ represent the same meaning as above.

R ^9C to R ^12C each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9C to R ^12C is a hydrocarbon having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent. Group, and at least one of R ^9C to R ^12C is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Each of Z ¹ and Z ² independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom which may have a substituent.]

[2] At least 1 selected from the group consisting of a colorant and a resin, and the colorant is a compound represented by formula (IA) described in [1], a compound represented by formula (IB), and a compound represented by formula (IC) A colored resin composition containing a dog.

[3] Further, the colored resin composition according to [2] containing a polymerizable compound and a polymerization initiator.

[4] A color filter formed from the colored resin composition according to [2] or [3].

[5] A display device including the color filter described in [4].

According to the present invention, a novel compound capable of forming a color filter excellent in heat resistance is provided.

Best mode for carrying out the invention

<Compound>

The compound according to the present invention is a compound represented by formula (IA) (hereinafter sometimes referred to as compound (IA)), a compound represented by formula (IB) (hereinafter referred to as compound (IB)), or It is a compound represented by formula (IC) (hereinafter, it may be referred to as a compound (IC)). Hereinafter, the present invention will be described in detail using formula (IA), formula (IB), or formula (IC), but in the compound (IA), compound (IB), or compound (IC), formula (IA), formula (IB), or a resonance structure of formula (IC) is included, and furthermore, each group in formula (IA), formula (IB), formula (IC), or their resonance structural formula is a single carbon-carbon bond or a single carbon-nitrogen bond. Compounds obtained by rotating around the coupling axis are also included.

<<Compound (IA)>>

A compound represented by formula (IA).

[In formula (IA),

Each of R ¹ to R ⁸ independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

R ^9A to R ^12A each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9A to R ^12A is a hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent to be.

QA ⁿ⁺ represents an n-valent metal ion.

n represents an integer of 2 or more.

bA represents the number of QA ⁿ⁺ .

When the total of negative charges included in R ¹ to R ⁸ and R ^9A to R ^12A is kA, aA is (n×bA)/kA.]

The alkyl group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ may be linear, branched or cyclic. As a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, heptadecyl group , Undecyl group, etc. are mentioned. As a cyclic alkyl group, a cyclopropyl group, 1-methylcyclopropyl group, cyclopentyl group, cyclohexyl group, 1, 2-dimethylcyclohexyl group, cyclooctyl group, 2, 4, 6-trimethylcyclohexyl group, 4- Cyclohexylcyclohexyl group, etc. are mentioned.

As the substituent of the C1-C20 alkyl group represented by R ¹ to R ⁸ , halogen atoms such as fluorine atom, chlorine atom and iodine; hydroxy group; -NR ^a R ^b (R ^a and R ^b are each independently, It is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; Etc.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include a group in which -O- is bonded to the bonding hand of the alkyl group having 1 to 20 carbon atoms. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy Period, 2-ethylhexyloxy group, etc. are mentioned.

As the substituent of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ , halogen atoms such as fluorine atom, chlorine atom and iodine; hydroxy group; -NR ^c R ^d (R ^c and R ^d are each independently , A hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group Etc.;

In the compound (IA), among R ¹ to R ⁸ , it is particularly preferable that R ¹ to R ⁴ are hydrogen atoms. In addition, R ⁵ to R ⁸ are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a hydrogen atom Or it is more preferable that it is a hydroxy group.

In the compound (IA), it is preferable that 2 to 4 of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are each independently a hydroxy group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A include an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, and saturated is preferable. Further, the C1-C20 aliphatic hydrocarbon group may be linear, branched or cyclic, and linear or branched is preferable.

Examples of linear or branched aliphatic hydrocarbons having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, 1-propenyl group, 2-propenyl group ( Allyl group), such as a linear aliphatic hydrocarbon group; branched chain aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and the like. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 15, more preferably 1 to 10.

The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 8, more preferably 3 to 6.

The methylene group contained in the C1-C20 aliphatic hydrocarbon group may be substituted with -O-. As a group in which the methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, a group represented by the following formula is exemplified. In the following formula, * represents a bond hand.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, and a naphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 16, more preferably 6 to 12, and still more preferably 6 to 9.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A may have a substituent, and as the substituent, -CO ₂ ^- ; carboxy group; -SO ₃ ^- ; -CONZ ¹ Z ² (Z ¹ and Z ² are, Each independently represents a C1-C10 hydrocarbon group or a hydrogen atom which may have a substituent); A halogen atom such as a fluorine atom, a chlorine atom, and iodine; An alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; Alkoxycarbonyl groups having 1 to 10 carbon atoms, such as a hydroxy group; a sulfamoyl group; a methoxycycarbonyl group and an ethoxycarbonyl group; and the like.

In the substituent-CONZ ¹ Z ² , examples of the hydrocarbon group having 1 to 10 carbon atoms represented by Z ¹ and Z ² include an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

The aliphatic hydrocarbon group having 1 to 10 carbon atoms may be either saturated or unsaturated. Further, the aliphatic hydrocarbon group having 1 to 10 carbon atoms may be linear, branched, or cyclic.

Specific examples of the C1-C10 aliphatic hydrocarbon group and the C6-C10 aromatic hydrocarbon group include those having 1 to 10 carbon atoms among the hydrocarbon groups having 1 to 20 carbon atoms represented by R ^9A to R ^12A .

Substituent-CONZ ^{1 In} Z ² , the hydrocarbon group having 1 to 10 carbon atoms represented by Z ¹ and Z ² may have a substituent, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, and iodine; methoxy group, ethoxy group Alkoxy carbonyl groups having 1 to 10 carbon atoms, such as alkoxy groups having 1 to 10 carbon atoms; hydroxy groups; sulfamoyl groups; methoxycarbonyl groups and ethoxycarbonyl groups; and the like.

At least one of R ^9A to R ^12A is a hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent. It is preferable that the hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent has 1 -CO ₂ ^- , preferably 1 to 2, more preferably 1. In addition, it is preferable that the -CO ₂ ^- is bonded to at least the terminal of the hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent. As a C1-C20 hydrocarbon group which has such -CO ₂ ^- as a substituent, a group represented by the following formula is mentioned, for example. In the following formula, * represents a bond hand.

It is preferable that at least one of R ^9A to R ^12A is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The aromatic hydrocarbon group having 6 to 20 carbon atoms which may have the substituent is preferably a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group or a di(2,2-dimethylpropyl)phenyl group, and more preferably 2,4 -Dimethylphenyl group or 2,4,6-trimethylphenyl group.

In compound (IA), even if R ^9A and R ^12A are each independently a hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent, and R ^10A and R ^11A each independently have a substituent It is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of ^n- valent metal ions represented by QA ⁿ⁺ include alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and barium ions; titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, and copper ions. Transition metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and bismuth ions; and the like. QA ⁿ⁺ is preferably an alkaline earth metal ion, more preferably a barium ion.

n is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and even more preferably 2.

Compound (IA) is electrically neutral, and when the total of negative charges contained in R ¹ to R ⁸ and R ^9A to R ^12A is kA, aA is (n×bA)/kA.

Further, bA is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

In addition, kA refers to the sum of -CO ₂ ^- contained in the formula (IA) when the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A does not have -SO ₃ ^- as a substituent, and preferably 1 They are -5, more preferably 2-4, still more preferably 2.

Examples of the compound (IA) include compounds represented by formulas (IA-1) to (IA-108) shown in Tables 1-2.

Compound (IA) is,

Preferably it is a compound represented by formula (IA-1) to formula (IA-54),

More preferably, it is a compound represented by formula (IA-1) to formula (IA-18),

More preferably, it is a compound represented by formula (IA-1)-formula (IA-3).

In Tables 1 to 2, ph1 to ph6 represents a group represented by the following formula (* means a bond).

In Tables 1-2, ca1-ca6 represents a group represented by the following formula (* means a bond).

<<Compound (IB)>>

A compound represented by formula (IB).

[In formula (IB), R ¹ to R ⁸ represent the same meaning as above.

R ^9B to R ^12B each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9B to R ^12B is an aliphatic hydrocarbon having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent. It is.

QB ⁿ⁺ represents a hydrone or an n-valent metal ion.

n represents an integer of 2 or more.

bB represents the number of QB ⁿ⁺ .

When the sum of -SO ₃ ^- contained in R ¹ to R ⁸ and R ^9B to R ^12B is kB, aB is (n×bB)/kB.]

In the compound (IB), among R ¹ to R ⁸ , it is particularly preferable that R ¹ to R ⁴ are hydrogen atoms. In addition, R ⁵ to R ⁸ are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a hydrogen atom Or it is more preferable that it is a hydroxy group.

In the compound (IB), it is preferable that 2 to 4 of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are each independently a hydroxy group. In particular, it is preferable that R ⁵ and R ⁸ are a hydroxy group and R ⁶ and R ⁷ are a hydrogen atom from the viewpoint of good heat resistance and light resistance.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9B to R ^12B include the same hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A , and the preferred range of carbon atoms is also the same.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^9B to R ^12B may have a substituent, and examples of the substituent include -SO ₃ ^- ; halogen atoms such as fluorine atom, chlorine atom and iodine; carbon number 1 such as methoxy group and ethoxy group And an alkoxycarbonyl group having 1 to 10 carbon atoms such as an alkoxy group of to 10; a hydroxyl group; a sulfamoyl group; a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

At least one of R ^9B to R ^12B is an aliphatic hydrocarbon group having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent. It is preferable that the aliphatic hydrocarbon group having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent has 1 -SO ₃ ^- , preferably 1 to 2, more preferably 1. In addition, the -SO ₃ ^- is, -SO ₃ ^- is preferably bonded to at least the terminal of an aliphatic hydrocarbon group of 1 to 20 carbon atoms having as the substituent. As the C1-C20 aliphatic hydrocarbon group which has such -SO ₃ ^- as a substituent, a group represented by the following formula is mentioned, for example. In the following formula, * represents a bond hand.

It is preferable that at least one of R ^9B to R ^12B is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The aromatic hydrocarbon group having 6 to 20 carbon atoms which may have the substituent is preferably a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group or a di(2,2-dimethylpropyl)phenyl group, and more preferably 2,4 -Dimethylphenyl group or 2,4,6-trimethylphenyl group.

In the compound (IB), R ^9B and R ^12B are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent, and R ^10B and R ^11B each independently have a substituent It is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present.

Examples of the n-valent metal ion represented by QB ⁿ⁺ include the same as the n-valent metal ion represented by QA ⁿ⁺ . QB ⁿ⁺ is preferably a hydrone, an alkaline earth metal ion, or a typical metal ion, more preferably a hydrone, a barium ion, a magnesium ion, or an aluminum ion. From the viewpoint of heat resistance and light resistance, a hydrone, barium or aluminum ion is preferable.

In addition, when the ^{n +} QB is high drones, high-art drones -SO ₃ ^- is present with a -SO ₃ H.

The preferable range of n is the same as above.

Compound (IB) is electrically neutral, and when the total of -SO ₃ ^- contained in R ¹ to R ⁸ and R ^9B to R ^12B is k, aB is (n×bB)/kB.

Further, bB is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

Further, kB is preferably 1 to 5, more preferably 2 to 4, and still more preferably 2.

Examples of the compound (IB) include compounds represented by formulas (IB-1) to (IB-432) shown in Tables 3 to 8.

Compound (IB) is,

Preferably, formula (IB-1) to formula (IB-54), formula (IB-109) to formula (IB-162), formula (IB-217) to formula (IB-270), and formula (IB-325 ) Is a compound represented by formula (IB-378),

More preferably, formula (IB-37)-formula (IB-54), formula (IB-145)-formula (IB-162), formula (IB-253)-formula (IB-270), formula (IB- 361) is a compound represented by formula (IB-378),

More preferably, formulas (IB-37) to formulas (IB-39), formulas (IB-145) to formulas (IB-147), formulas (IB-253) to formulas (IB-255), and formulas (IB- It is a compound represented by 361)-formula (IB-363).

In Tables 3 to 8, ph1 to ph6 represent the same groups as described above.

In Tables 3-8, su1-su6 represents a group represented by the following formula (* means a bond).

<<Compound (IC)>>

A compound represented by formula (IC).

[In formula (IC), R ¹ to R ⁸ represent the same meaning as above.

R ^9C to R ^12C each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9C to R ^12C is a hydrocarbon having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent. Group, and at least one of R ^9C to R ^12C is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Each of Z ¹ and Z ² independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom which may have a substituent.]

In the compound (IC), among R ¹ to R ⁸ , R ¹ to R ⁴ are particularly preferably hydrogen atoms. In addition, R ⁵ to R ⁸ are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and a hydrogen atom Or it is more preferable that it is a hydroxy group.

In the compound (IC), it is preferable that 2 to 4 of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are each independently a hydroxy group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9C to R ^12C include the same hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A , and the preferred range of carbon atoms is also the same.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^9C to R ^12C may have a substituent, and as the substituent, -CONZ ¹ Z ² ; halogen atoms such as fluorine atom, chlorine atom and iodine; carbon number such as methoxy group and ethoxy group A 1-10 alkoxy group; a hydroxy group; a sulfamoyl group; a C1-C10 alkoxycarbonyl group, such as a methoxycarbonyl group and an ethoxycarbonyl group; etc. are mentioned.

Z ¹ and Z ² represent the same meaning as above.

In the compound (IC), Z ¹ and Z ² are each independently a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent or a hydrogen atom, and a hydrocarbon group having 1 to 3 carbon atoms or hydrogen which may have a substituent An atom is more preferable, and a hydrogen atom is more preferable.

At least one of R ^9C to R ^12C is a hydrocarbon group having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent. It is preferable that the hydrocarbon group having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent has 1 to 2, more preferably 1 -CONZ ¹ Z ² . Further, -CONZ ¹ Z ² are preferably bonded to at least the end of the hydrocarbon group having 1 to 20 carbon atoms, a -CONZ ¹ Z ² as a substituent. As a C1-C20 hydrocarbon group which has such -CONZ ¹ Z ² as a substituent, a group represented by the following formula is mentioned, for example. In the following formula, * represents a bond hand.

At least one of R ^9C to R ^12C is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The aromatic hydrocarbon group having 6 to 20 carbon atoms which may have the substituent is preferably a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group or a di(2,2-dimethylpropyl)phenyl group, and more preferably 2,4 -Dimethylphenyl group or 2,4,6-trimethylphenyl group.

In the compound (IC), R ^9C and R ^11C are each independently a hydrocarbon group having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent, and R ^10C and R ^12C each independently have a substituent It is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present.

Examples of the compound (IC) include compounds represented by formulas (IC-1) to (IC-108) shown in Tables 9 to 10.

Compound (IC) is,

Preferably it is a compound represented by formula (IC-1) to formula (IC-54),

More preferably, it is a compound represented by formula (IC-1) to formula (IC-18),

More preferably, it is a compound represented by formula (IC-1)-formula (IC-3).

In Tables 9 to 10, ph1 to ph6 represent the same groups as described above.

In Tables 9-10, bm1-bm6 represents a group represented by the following formula (* means a bond hand).

The compound represented by the formula (IA) and the compound represented by the formula (IB) in the case of a metal ion having Q ⁿ⁺ = n correspond to a compound represented by the formula (pt5) in the following formula. In addition, the compound represented by the formula (IB) and the compound represented by the formula (IC) in the case of Q ^{n +} =hydrone corresponds to the compound represented by the formula (pt4) in the following formula.

The compound represented by formula (pt5) and the compound represented by formula (pt4) can be produced by the following method.

The compound represented by formula (pt5) is prepared by reacting a compound represented by formula (pt4) with a halide (preferably chloride) containing an n-valent metal ion, acetate, phosphate, sulfate, silicate, or cyanide. can do.

The compound represented by formula (pt4) can be produced by reacting a compound represented by formula (pt1), a compound represented by formula (pt2), and a compound represented by formula (pt3). In this reaction, the total amount of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is preferably 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt3).

[In formulas (pt1) to formulas (pt2) and formulas (pt4) to formulas (pt5), R ¹ to R ⁸ are the same as above, and R ^9X to R ^12X are R ^9A to R ^12A and R ^9B to R ^12B or R ^9C to R ^12C is represented, QX ⁿ⁺ represents QA ⁿ⁺ , QB ⁿ⁺ , or QC ⁿ⁺ , aX represents aA, aB, or aC, bX represents bA, bB, or bC And R ^9A to R ^12A , R ^9B to R ^12B , R ^9C to R ^12C , aA, aB, aC, bA, bB, and bC are the same as above, and R ^9aX to R ^12aX are each independently a substituent It represents a C1-C20 hydrocarbon group which may have.]

<Colored resin composition>

The colored resin composition of the present invention contains a colorant (A) and a resin (B), and the colorant (A) is a compound represented by formula (IA), a compound represented by formula (IB), and formula (IC). It includes at least one selected from the group consisting of compounds.

It is preferable that the colored resin composition of the present invention further contains a polymerizable compound (C) and a polymerization initiator (D).

The colored resin composition of the present invention may further contain a polymerization initiator (D1), a solvent (E), and a leveling agent (F).

In the present specification, the compounds exemplified as each component can be used alone or in combination of multiple types unless otherwise specified.

<Coloring agent (A)>

The colored resin composition of the present invention contains at least one selected from the group consisting of a compound (IA), a compound (IB), and a compound (IC) as the colorant (A). The content of the compound (IA), compound (IB), and/or compound (IC) is preferably 0.1 to 150 parts by mass, more preferably 0.5 to 100 parts by mass, based on 100 parts by mass of the resin (B), It is more preferable that it is 1 to 80 mass parts.

The content rate of the total of the compound (IA), the compound (IB), and the compound (IC) is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% by mass or more in the total amount of the colorant (A). It is more preferable.

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

The dye (A1) is not particularly limited, and a known dye can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes and the like. Examples of dyes include compounds classified as having colors other than pigments in the color index (published by The Society of Dyers and Colorists), and known dyes described in dye notes (color dyes). . In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye (however, , Compound (IA), compound (IB), and compound (IC) are excluded), acridine dye, styryl dye, coumarin dye, quinoline dye, and nitro dye. Among these, organic solvent-soluble dyes are preferred.

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

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

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. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ；

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;

C.I. Green pigments, such as Pigment Green 7, 36, and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments, such as pigment black 1 and 7; etc. are mentioned.

The content rate of the colorant (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and still more preferably 1 to 50% by mass with respect to the total amount of the solid content of the colored resin composition.

Here, the "total amount of solid content" in this specification refers to the amount excluding the content of the solvent from the total amount of the colored resin composition. The total amount of solid content and the content of each component thereto can be measured by known analysis means such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but it is preferably an alkali-soluble resin, and at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "(a)" A resin having a structural unit derived from) is more preferable. Resin (B) is a structural unit derived from a monomer (b) having an ethylenically unsaturated bond and a cyclic ether structure having 2 to 4 carbon atoms (hereinafter sometimes referred to as ``(b)''), (a) A structural unit derived from a monomer (c) copolymerizable with (however, (a) and (b) are different) (hereinafter sometimes referred to as ``(c)''), and having an ethylenically unsaturated bond in the side chain It is preferable to have at least one kind of structural unit selected from the group consisting of structural units.

As (a), specifically, for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono [2-(meth)acrylic Royloxyethyl] and the like, preferably acrylic acid, methacrylic acid, and 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 an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth)acryloyloxy group Is preferred.

In addition, in this specification, "(meth)acrylic acid" represents at least 1 type selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" 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-epoxytricyclo[ 5.2.1.0 ^2,6 ] Decyl (meth) acrylate, 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 ]Decane-8-yl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene , Vinyl toluene, and the like, preferably styrene, vinyl toluene, 2-hydroxyethyl (meth) acrylate, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, etc. Do.

Resin having a structural unit having an ethylenically unsaturated bond in the side chain, (b) is added to the copolymer of (a) and (c), or (a) is added to the copolymer of (b) and (c). It can be manufactured by making it. The resin may be a resin in which (a) is added to the copolymer of (b) and (c) and further reacted with carboxylic 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 dispersion degree [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 the resin (B), in terms of solid content, is preferably 20 to 170 mg-KOH/g, more preferably 30 to 150 mg-KOH/g, and still more preferably 40 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content rate of the resin (B) is preferably 30 to 99.9 mass%, more preferably 50 to 99.5 mass%, and still more preferably 70 to 99 mass% with respect to the total amount of the solid content of the colored resin composition.

When the colored resin composition of the present invention contains a polymerizable compound (C) and a polymerization initiator (D), the content rate of the resin (B) is preferably 7 to 65 mass% with respect to the total amount of the solid content of the colored resin composition. And more preferably 13 to 60 mass%, still more preferably 17 to 55 mass%.

<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 a compound having a polymerizable ethylenically unsaturated bond, and the like. It is a (meth)acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and , Dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

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 included, the content rate of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, further preferably based on the total amount of the solid content. It is 17 to 55% by mass.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. As a polymerization initiator generating an active radical, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfide) Panylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1- (4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2 -Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenylketone, 2, 4-bis(trichloromethyl)-6-piperonyl- 1, 3, 5-triazine, 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, 2, 2'-bis(2-chlorophenyl)-4, 4', 5, 5'-tetraphenylbiimi Dazole, 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 based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Hagi is 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, since there is a tendency that the sensitivity is increased and the exposure time is shortened, the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate polymerization of a polymerizable compound in which polymerization has been initiated by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

As the polymerization initiation aid (D1), 4,4'-bis(dimethylamino)benzophenone (commonly known as Mihiraz ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl thioxanthone, N-phenylglycine, and the like.

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester Solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule, and not -COO-), alcohol solvent (containing OH in the molecule,- Solvents that do not contain O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

As a solvent,

Ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and ester solvents such as γ-butyrolactone (in the molecule- Solvent containing COO- 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 (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, diethylene glycol monoethyl ether acetate, etc. Solvent containing -COO- and -O-);

Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, and cyclohexanone (including -CO- in the molecule, -COO Solvent not containing -);

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

Amide solvents such as N,N-dimethylformamide, N,N-polymethylacetamide, and N-methylpyrrolidone; and the like.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

When the solvent (E) is included, the content rate of the solvent (E) is preferably 60 to 95 mass%, and more preferably 65 to 92 mass% with respect to the total amount of the colored resin composition of the present invention. In other words, the total amount of the solid content of the colored resin composition is preferably 5 to 40% by mass, more preferably 8 to 35% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of application is improved, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be improved.

<Leveling agent (F)>

As the leveling agent (F), a silicone-based surfactant, a fluorine-based surfactant, a silicon-based surfactant having a fluorine atom, and the like can be mentioned. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Chemical Industries, Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (made by Momentive Performance Materials Japan Joint Company). .

Examples of the above fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florade (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, wing F171, wing F172, wing F173, wing F177, wing F183, wing F554, wing R30, copper RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (Mitsubishi Material Electronics Chemical Co., Ltd.), Surfron (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.), and the like.

Examples of the silicone-based surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in a molecule. Specifically, Megapack (registered trademark) R08, copper BL20, copper F475, copper F477 and copper F443 (manufactured by DIC Corporation), and the like can be mentioned.

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2 mass%, and more preferably 0.002 to 0.1 mass% with respect to the total amount of the colored resin composition. In addition, the content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

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

<Production method of colored resin composition>

The colored resin composition of the present invention includes a coloring agent (A) and a resin (B), and a polymerizable compound (C) used as needed, a polymerization initiator (D), a polymerization initiator aid (D1), a solvent (E), and leveling. It can be prepared by mixing the agent (F) and other ingredients.

<Production method of color filter>

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

When the colored resin composition contains at least one selected from the group consisting of a compound represented by formula (IA), a compound represented by formula (IB), and a compound represented by formula (IC), a color filter having particularly excellent heat resistance can be produced. I can. This color filter is useful as a color filter used in a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Mode for carrying out the invention

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited by these examples. In the examples,% and parts indicating content or amount of use are based on mass unless otherwise noted.

In the following, the structure of the compound was confirmed by mass spectrometry (LC; 1200 type manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

(Synthesis Example 1)

1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 parts, 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 55 parts, potassium hydroxide (Wako Pure Chemical Industries, Ltd.) ) Article) 51 parts, tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.5 parts, bis(tri-t-butylphosphine) palladium (manufactured by Aldrich Corporation) 2.3 parts, water 100 parts and toluene 1000 parts (Kanto Chemical Co., Ltd. product) was mixed and heated at 90 degreeC, stirring for 1 hour. After completion of the reaction, the organic layer was separated with water and ethyl acetate to separate the organic layer. And the organic layer was dried with magnesium sulfate, and the solvent was distilled off with an evaporator, and 113 parts of the compound represented by Formula (1A-1) were obtained.

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 258.2

Exact　Mass：+257.1

(Synthesis Example 2)

70 parts of the compound represented by formula (1A-1), 10 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) 53 parts and 700 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) are mixed, and 100 It heated while stirring at degreeC for 16 hours. After the reaction was completed, the solvent was distilled off, and 700 parts of hexane (manufactured by Kanto Chemical Co., Ltd.) were added to the obtained crude product, and the mixture was stirred for 2 hours to filter out the solid to obtain 90 parts of the compound represented by formula (1A-2). Got it.

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 372.2

Exact　Mass：+371.1

(Synthesis Example 3)

34 parts of the compound represented by formula (1A-2) were dissolved in 340 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.), cooled to 0°C, and 92 parts of boron tribromide (manufactured by Tokyo Chemical Co., Ltd.) were added dropwise. After completion of the dropwise addition, the temperature was raised to 10° C. and stirred for 3 hours. Water was added to extract the organic layer, and the solvent was distilled off to obtain 89 parts of crude product A. The crude product A contained 44% of the compound represented by formula (1A-3) and 53% of the compound represented by formula (1A-3-1).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 344.2

Exact　Mass: +343.1　 formula (1A-3)

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 330.2

Exact　Mass: +329.1　 formula (1A-3-1)

(Synthesis Example 4)

89 parts of crude product A were dissolved in 370 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, 51 parts of thionyl chloride (manufactured by Tokyo Chemical Co., Ltd.) were added. The mixture was stirred at room temperature at 23°C for 16 hours, and after the reaction was completed, water was added to evaporate the solvent, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 53 parts of the compound represented by the formula (1A-3).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 344.2

Exact　Mass：+343.1

(Synthesis Example 5)

53 parts of the compound represented by formula (1A-3) was dissolved in 530 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0°C, and then 460 parts of borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) It was dripped and stirred at 20 degreeC for 5 hours after completion|finish of dripping. After completion of the reaction, water was added, and the crude product obtained by distilling off the solvent was separated and purified by column chromatography to obtain 25 parts of the compound represented by formula (1A-4).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 330.3

Exact　Mass：+329.2

4 parts of the compound represented by formula (1A-4), lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 2.5 parts, methanol (manufactured by Kanto Chemical Co., Ltd.) 20 parts, tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) ) 20 parts were added, and it stirred at room temperature 23 degreeC for 5 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 1.7 parts of the compound represented by formula (1A-5).

Identification: (mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 316.1

Exact　Mass：+315.2

(Synthesis Example 6)

1.7 parts of the compound represented by formula (1A-5) and 0.3 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) toluene (manufactured by Kanto Chemical Co., Ltd.) It dissolved in 65 parts and 17 parts of n-butanol (made by Kanto Chemical Co., Ltd.), and heated at 120 degreeC, stirring for 2 hours. After completion of the reaction, the crude product obtained by distilling off the solvent was separated and purified by silica gel column chromatography to obtain 0.85 parts of the compound represented by the formula (1A-6).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 709.3

Exact　Mass：+708.3

[Example 1]

1.0 part of the compound represented by Formula (1A-6) was added and dissolved in 25 parts of 0.8% sodium hydroxide aqueous solution, and the aqueous solution 1 was prepared. Separately, a solution (aqueous solution 2) in which 1.7 parts of barium chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 10 parts of water was prepared, and the aqueous solution 2 was slowly added to the aqueous solution 1 at 23°C, followed by stirring for 30 minutes. did. After completion of the reaction, the solid obtained by suction filtration was rinsed and washed with water and acetone. The washed solid was dried under reduced pressure at 60° C. for 12 hours to obtain 1.2 parts of a compound represented by formula (1A-7).

(Synthesis Example 7)

26.0 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.8 parts of 1,4-butane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.) in a nitrogen atmosphere, 5.0 parts of toluene (manufactured by Kanto Chemical Corporation) And heated at 100° C. for 3 hours while stirring. After completion of the reaction, toluene was distilled off with an evaporator, and then 50 parts of a 10% aqueous sodium hydroxide solution was added to precipitate a solid. After obtaining a solid by suction filtration, the solid was rinsed and washed with water and hexane. It dried under reduced pressure at 60 degreeC for 12 hours, and 20.0 parts of the compounds represented by Formula (1B-1) were obtained. The yield was 99%.

Identification: (mass spectrometry) ionization mode = ESI-: m/z = [M-Na] ⁺ 256.2

Exact　Mass：+279.09

(Synthesis Example 8)

12.8 parts of the compound represented by formula (1B-1), 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts, palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3 parts, 0.47 parts of tri-tert-butylphosphine 1.0M hexane solution (Wako Pure Chemical Industries, Ltd.) was dissolved in 200 parts of toluene (Tokyo Chemical Industry Co., Ltd.), and stirred at room temperature for 10 minutes under a nitrogen atmosphere. 9.0 parts of sodium tert-butoxy (Tokyo Chemical Industry Co., Ltd.) was added there, and it heated, stirring at 110 degreeC for 4 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and then separated with water and ethyl acetate to separate the organic layer. And the organic layer was dried with magnesium sulfate, ethyl acetate was distilled off with an evaporator, and 6.1 parts of the compound represented by Formula (1B-2) were obtained. The yield was 32%.

Identification: (mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 394.5

Exact　Mass：393.16

(Synthesis Example 9)

9.8 parts of the compound represented by formula (1B-2) were dissolved in 27.0 parts of acetic acid (Wako Pure Chemical Industries, Ltd.) and 27.0 parts of hydrobromic acid (Wako Pure Chemical Industries, Ltd.), and stirred at 50°C for 5 hours. After completion of the reaction, acetic acid and hydrobromic acid were distilled off with an evaporator. After separating with ethyl acetate and water to separate the organic layer, the organic layer was concentrated to obtain 9.0 parts of the compound represented by the formula (1B-3). The yield was 98%.

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 366.2

Exact　Mass：+365.13

[Example 2]

7.0 parts of the compound represented by formula (1B-3) and 1.0 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) 1-butanol (Kanto Chemical Co., Ltd.) It dissolved in 70 parts and 49 parts of toluene (made by Kanto Chemical Co., Ltd.), and stirred at 110 degreeC for 3 hours. After completion of the reaction, 49 parts of hexane was added to precipitate a solid, and then a solid was obtained by suction filtration. The obtained solid was dried under reduced pressure at 60° C. for 12 hours to obtain 4.0 parts of a compound represented by formula (1B-4). The yield was 27%.

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 809.2

Exact　Mass：+808.23

[Example 3]

1.0 part of the compound represented by formula (1B-4) was added to 6.0 parts of methanol, and a solution (solution 3) in which the compound represented by formula (1B-4) was dissolved was prepared. Separately, a solution (solution 4) in which 7.5 parts of barium chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 20 parts of water was prepared, and solution 4 was slowly added to solution 3 at room temperature, followed by stirring for 30 minutes. After completion of the reaction, the solid obtained by suction filtration was rinsed and washed with water and acetone. It dried under reduced pressure at 60 degreeC for 12 hours, and obtained 1.0 part of a compound represented by Formula (1B-5). The yield was 75%.

[Example 4]

In Example 3, in the same manner as in Example 3, except that 10.6 parts of aluminum sulfate 14-18 hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of barium chloride dihydrate, represented by formula (1B-6). 1.3 parts of compounds were obtained. The yield was 99%.

(Synthesis Example 10)

In Synthesis Example 8, in the same manner as in Synthesis Example 8, except that 8.0 parts of 3-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1-bromo-3,5-dimethoxybenzene, the formula 9.9 parts of the compound represented by (1B-7) were obtained. The yield was 52%.

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 350.5

Exact　Mass：349.13

[Example 5]

In Example 2, the compound represented by the formula (1B-8) in the same manner as in Example 2, except that 8.0 parts of the compound represented by the formula (1B-7) was used instead of the compound represented by the formula (1B-3). 5.7 parts were obtained. The yield was 68%.

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 777.5

Exact　Mass：+776.2

[Example 6]

In Example 3, a compound represented by formula (1B-9) in the same manner as in Example 3, except that 1.0 part of the compound represented by formula (1B-8) was used instead of the compound represented by formula (1B-4). 0.7 parts were obtained. The yield was 51%.

[Example 7]

In Example 6, in the same manner as in Example 6, except for using 2.3 parts of aluminum sulfate 14-18 hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) instead of barium chloride dihydrate, represented by formula (1B-10). 0.7 parts of compounds were obtained. The yield was 52%.

[Example 8]

In Example 6, in the same manner as in Example 6 except that 1.2 parts of magnesium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of barium chloride dihydrate, 0.3 parts of the compound represented by formula (1B-11) Got it. The yield was 22%.

(Synthesis Example 11)

1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.0 parts, 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.2 parts, potassium hydroxide 10.3 parts, bis (tri -tert-butylphosphine)palladium (0) 0.47 parts, and tetrabutylammonium bromide 0.30 parts dissolved in 200 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 20 parts of water under a nitrogen atmosphere, while stirring at 90°C for 16 hours Heated. After completion of the reaction, the organic solvent was distilled off with an evaporator to obtain 25 parts of the compound represented by formula (1C-1).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 258.2

Exact　Mass：+257.1

(Synthesis Example 12)

25 parts of the compound represented by formula (1C-1) and 19.0 parts of succinic acid monomethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 250 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) under a nitrogen atmosphere, and at 100°C for 16 hours Heated while stirring. After completion of the reaction, water was added to separate the organic layer, concentrated with an evaporator, and separated and purified by silica gel column chromatography to obtain 22 parts of a compound represented by formula (1C-2).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 372.2

Exact　Mass：+371.2

(Synthesis Example 13)

21.0 parts of the compound represented by formula (1C-2) are dissolved in 210 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) in a nitrogen atmosphere, and 280 parts of boron tribromide 1M dichloromethane solution (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved at 0°C After adding at, it heated up to 10 degreeC and stirred for 6 hours. After completion of the reaction, water was added to separate the organic layer, dried over magnesium sulfate, and concentrated with an evaporator to obtain a crude product B. The crude product B contained 49% of the compound represented by formula (1C-3) and 34% of the compound represented by formula (1C-3-1).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 344.2

Exact　Mass: +343.1　 formula (1C-3)

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 330.2

Exact　Mass: +329.1　 formula (1C-3-1)

(Synthesis Example 14)

23 parts of crude product B was added in a nitrogen atmosphere to 200 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), cooled to 0°C, and 18 parts of thionyl chloride were added dropwise. After the dropwise addition, the mixture was heated to room temperature and stirred for 5 hours. After completion of the reaction, water was added to separate the organic layer. It dried over magnesium sulfate, the solvent was distilled off with an evaporator, and it separated and refine|purified by silica gel column chromatography, and obtained 16 parts of the compound represented by Formula (1C-3).

(Synthesis Example 15)

After dissolving 16.0 parts of the compound represented by formula (1C-3) in 160 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) in a nitrogen atmosphere and cooling to 0°C, a solution of borane 1M tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) Article) 140 parts were dripped. After completion of the dropwise addition, the temperature was raised to 20°C and stirred for 5 hours. After adding water, the organic layer was separated, concentrated with magnesium sulfate, the solvent was distilled off with an evaporator, and separated and purified by silica gel column chromatography to obtain 6 parts of the compound represented by the formula (1C-4).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 330.3

Exact　Mass：+329.2

(Synthesis Example 16)

5 parts of the compound represented by formula (1C-4) was dissolved in 5 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and 20 parts of ammonia 4M methanol solution was added, followed by heating in an autoclave at 60°C for 48 hours while stirring. After completion of the reaction, the solvent was concentrated with an evaporator, and separated and purified by silica gel column chromatography to obtain 3 parts of the compound represented by the formula (1C-5).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 315.2

Exact　Mass：+314.2

[Example 9]

3 parts of the compound represented by formula (1C-5) and 0.5 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) 20 parts of toluene under nitrogen atmosphere (Kanto Chemical It dissolved in 5 parts (manufactured by Co., Ltd.) and 1-butanol (manufactured by Kanto Chemical Co., Ltd.) and heated while stirring at 120°C for 2 hours. After completion of the reaction, the solvent was distilled off with an evaporator, 40 parts of tetrahydrofuran were added, stirred for 1 hour, filtered and dried to obtain 2.4 parts of the compound represented by the formula (1C-6).

Identification: (mass spectrometry) Ionization mode = ESI+: m/z = [M+H] ⁺ 707.4

Exact　Mass：+706.3

(Resin Synthesis Example 1)

In a flask equipped with a reflux condenser, a dropping lot, and a stirrer, nitrogen was allowed to flow in an appropriate amount and replaced with a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85°C while stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylic A mixed solution of 225 parts of a mixture of rates (the mixing ratio is 1:1), 81 parts of vinyl toluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a solution in which 30 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropping of the initiator solution, the flask was kept at 85°C for 4 hours, then cooled to room temperature, and a copolymer having a B-type viscosity (23°C) of 246 mPa·s and a solid content of 37.5% (resin (B-1)) I got a solution. The weight average molecular weight Mw of the resulting copolymer was 10600, the dispersion degree was 2.01, and the solid content acid value was 115 mg-KOH/g. Resin (B-1) has the following structural units.

(Resin Synthesis Example 2)

In a flask equipped with a reflux condenser, a dropping lot, and a stirrer, an appropriate amount of nitrogen was flowed and replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 80°C while stirring. Subsequently, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] decane-9-ylacrylic A mixed solution of 289 parts of a mixture of rates (the mixing ratio is 1:1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution in which 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropping was completed, the flask was kept at 80°C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) solution having a B-type viscosity (23°C) of 125 mPa·s and a solid content of 35.1%. . The resulting copolymer had a weight average molecular weight Mw of 9200, a dispersion degree of 2.08, and a solid acid value of 77 mg-KOH/g. Resin (B-2) has the following structural units.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene of the resin was performed under the following conditions by the GPC method.

Equipment　　　　　　; HLC-8120 GPC (manufactured by Tosoh Corporation)

Column　　　　　；TSK-GELG2000HXL

Column temperature　　　；40℃

Solvent　　　　　　； THF

Flow velocity　　　　　　; 1.0mL/min

Test solution solid content concentration; 0.001 to 0.01 mass%

Injection volume　　　　　；50μL

Detector　　　　　；RI

Standard substances for calibration　；TSK　STANDARD　POLYSTYRENE

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

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

Preparation of dispersion (P-1)

5 parts of the compound represented by formula (1A-7), 5 parts of dispersant, 4 parts (solid content) of resin (B-1), 76 parts of propylene glycol monomethyl ether acetate, and 10 parts of diacetone alcohol are mixed therein. 300 parts of zirconia beads having a diameter of 0.2 μm were put, and shaken for 3 hours using a paint conditioner (manufactured by LAU) to remove the zirconia beads to prepare a dispersion (P-1).

With the composition shown in Table 11, dispersions (P-2) to (P-9) were produced in the same manner as in preparation of dispersion (P-1).

In Table 11, each component represents the following compounds.

Coloring agent (A-1): Compound represented by formula (1A-7)

Coloring agent (A-2): Compound represented by formula (1B-4)

Coloring agent (A-3): Compound represented by formula (1B-5)

Coloring agent (A-4): Compound represented by formula (1B-6)

Coloring agent (A-5): Compound represented by formula (1B-8)

Coloring agent (A-6): Compound represented by formula (1B-9)

Coloring agent (A-7): Compound represented by formula (1B-10)

Coloring agent (A-8): Compound represented by formula (1B-11)

Coloring agent (A-9): Compound represented by formula (1C-6)

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

Solvent (E-1): Propylene glycol monomethyl ether acetate

Solvent (E-2): Diacetone alcohol

Dispersant (G-1): Acrylic dispersant

[Examples 10 to 18, Comparative Example 1]

[Preparation of colored resin composition]

Each component was mixed so that it might become the composition shown in Table 12, and the colored resin composition was obtained.

In Table 12, each component represents the following compounds.

Coloring agent (A-X): Compound represented by formula (X)

Resin (B-2): Resin (B-2) (solid content conversion)

Solvent (E-1): Propylene glycol monomethyl ether acetate

Solvent (E-2): Diacetone alcohol

Solvent (E-3): Chloroform

Leveling agent (F-1): Polyether modified silicone oil (Toray Dow Corning Co., Ltd. "Toray Silicone SH8400")

<Production 1 of color filter (color coating)>

After applying the colored resin composition on a 5 cm-square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, it was prebaked at 100°C for 3 minutes to obtain a colored coating film.

<Measurement of chromaticity>

The chromaticity of the colored coating film is determined from the spectroscopy measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.) and from the characteristic function of the C light source, the xy chromaticity coordinates (x, y) and the stimulation value Y.

<heat resistance evaluation>

The obtained colored coating film was heated in an oven at 230°C for 2 hours. The chromaticity was measured before and after heating, and the color difference ΔEab* was calculated from the measured value by the method described in JIS 　Z　8730:2009 (7. Calculation method of color difference), and the results are shown in Table 13. ΔEab* means that the smaller the color change is. In addition, if the heat resistance of the colored coating film is good, it can be said that the colored pattern produced from the same colored resin composition also has good heat resistance.

[Examples 19-25]

[Preparation of colored resin composition]

Each component was mixed so that it might become the composition shown in Table 14, and the colored resin composition was obtained.

In Table 14, each component represents the following compounds.

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

Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (PBG-327; oxime compound; resident powerful electronic new material (subject)

Other symbols represent the same as above.

<Production 2 of color filter (colored coating film) and evaluation of heat resistance>

After applying the colored resin composition by spin coating on a 5 cm-square glass substrate (Eagle 2000; manufactured by Corning), it was prebaked at 100°C for 3 minutes to form a colored composition layer. After standing to cool, the colored composition layer formed on the substrate was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) at an exposure amount of 100 mJ/cm 2 (based on 365 nm) in an air atmosphere. After light irradiation, post-baking was performed for 30 minutes at 230 degreeC in an oven, and the colored coating film was obtained.

The chromaticity was measured before and after post-baking, and the color difference ΔEab* was calculated from the measured value by the method described in JIS 　Z　8730:2009 (7. Calculation method of color difference), and the results are shown in Table 15.

According to the compound of the present invention, a color filter excellent in heat resistance can be formed.

Claims (5)

Compound represented by formula (IA), formula (IB), or formula (IC)

[In formula (IA),
Each of R ¹ to R ⁸ independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and an alkoxy group having 1 to 20 carbon atoms which may have a substituent.
R ^9A to R ^12A each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9A to R ^12A is a hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent to be.
QA ⁿ⁺ represents an n-valent metal ion.
n represents an integer of 2 or more.
bA represents the number of QA ⁿ⁺ .
When the total of negative charges included in R ¹ to R ⁸ and R ^9A to R ^12A is kA, aA is (n×bA)/kA.]

[In formula (IB),
R ¹ to R ⁸ represent the same meaning as above.
R ^9B to R ^12B each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9B to R ^12B is an aliphatic hydrocarbon having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent. It is.
QB ⁿ⁺ represents a hydrone or an n-valent metal ion.
n represents an integer of 2 or more.
bB represents the number of QB ⁿ⁺ .
When the sum of -SO ₃ ^- contained in R ¹ to R ⁸ and R ^9B to R ^12B is kB, aB is (n×bB)/kB.]

[In formula (IC),
R ¹ to R ⁸ represent the same meaning as above.
R ^9C to R ^12C each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9C to R ^12C is a hydrocarbon having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent. Group, and at least one of R ^9C to R ^12C is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
Each of Z ¹ and Z ² independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom which may have a substituent.] A colorant and a resin are included, and the colorant contains at least one selected from the group consisting of a compound represented by formula (IA) according to claim 1, a compound represented by formula (IB), and a compound represented by formula (IC). Colored resin composition. The method of claim 2,
Further, a colored resin composition comprising a polymerizable compound and a polymerization initiator. A color filter formed from the colored resin composition according to claim 2 or 3. A display device comprising the color filter according to claim 4.