TW201938699A - Compound, colored resin composition, color filter and display device - Google Patents

Abstract

The present invention provides a compound and a colored resin composition, which are capable of forming a color filter and a display device, both of which have excellent heat resistance.

Description

Compound, colored resin composition, color filter and display device

This invention relates to a compound.

Display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, or solid-state imaging devices such as CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) sensors The color filter used in this is manufactured from a colored resin composition. As a coloring agent used in such a coloring resin composition, a compound represented by the formula (X) is known.

[Prior technical literature]
[Patent Literature]
[Patent Document 1] Japanese Patent Application Laid-Open No. 2015-86380

[Problems to be Solved by the Invention]

However, there is a case where a color filter formed of a coloring resin composition containing a conventionally known compound described above cannot sufficiently satisfy heat resistance. Therefore, the present invention provides a compound capable of forming a color filter having excellent heat resistance.
[Means for solving problems]

The present invention includes the following inventions.

[1] A compound represented by the formula (IA), (IB), or (IC):



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



[In formula (IB),
R ¹ to R ^{8 have the} same meanings as above;
R ^9B to R ^12B each independently represent a hydrocarbon group having 1 to 20 carbons which may have a substituent, and at least one of R ^9B to R ^12B is an aliphatic having 1 to 20 carbons having -SO ₃ ^- as a substituent Hydrocarbyl
QB ^{n +} represents a hydrogen positive ion or an n-valent metal ion;
n represents an integer of 2 or more;
bB represents the number of QB ^{n +} ;
When the total number of -SO ₃ ^- contained in R ¹ to R ⁸ and R ^9B to R ^12B is set to kB, aB is (n × bB) / kB]



[In formula (IC),
R ¹ to R ^{8 have the} same meanings as above;
R ^9C to R ^12C each independently represent a hydrocarbon group having 1 to 20 carbons which may have a substituent, and at least one of R ^9C to R ^12C is a hydrocarbon group having 1 to 20 carbons having -CONZ ¹ Z ² as a substituent 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;
Z ¹ and Z ² each independently represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms which may have a substituent]

[2] A colored resin composition comprising a colorant and a resin, wherein the colorant includes a compound represented by the formula (IA) as described in [1], a compound represented by the formula (IB), and a formula ( At least one selected from the group consisting of compounds represented by IC).

[3] The colored resin composition according to [2], further comprising a polymerizable compound and a polymerization initiator.

[4] A color filter formed of the colored resin composition as described in [2] or [3].

[5] A display device including the color filter according to [4].

[Effect of the invention]

According to the present invention, a novel compound capable of forming a color filter having excellent heat resistance can be provided.

<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 sometimes referred to as compound (IB)), or a formula ( IC) (hereinafter sometimes referred to as compound (IC)). Hereinafter, although the present invention is described in detail using formula (IA), formula (IB), or formula (IC), compound (IA), compound (IB), or compound (IC) also includes formula (IA), formula (IC) IB), or the resonance structure of the formula (IC), further includes having each group in the formula (IA), the formula (IB), the formula (IC), or the resonance structure formula surrounding a carbon-carbon single bond or A compound obtained by rotating a carbon-nitrogen single bond bond axis.

"Compound (IA)"

A compound represented by formula (IA).



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

The alkyl group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ may be any of linear, branched, and cyclic. Specific examples of the linear or branched alkyl group include methyl, ethyl, propyl, isobutyl, butyl, tertiary butyl, hexyl, heptyl, octyl, nonyl, Decyl, heptadecyl, undecyl and the like. Examples of the cyclic alkyl group include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, cyclooctyl, 2,4,6-tri Methylcyclohexyl, 4-cyclohexylcyclohexyl and the like.

Examples of the substituent of the alkyl group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include halogen atoms such as a fluorine atom, a chlorine atom, and iodine; a hydroxyl group; and -NR ^a R ^b (R ^a and R ^b are each independently Ground 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; 10 alkoxycarbonyl and the like.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include a group having -O- bonded to the bonding end of the alkyl group having 1 to 20 carbon atoms. Specific examples include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy, heptyl Oxy, octyloxy, 2-ethylhexyloxy and the like.

Examples of the substituent of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include a halogen atom such as a fluorine atom, a chlorine atom, and iodine; a hydroxyl group; and -NR ^c R ^d (each of R ^c and R ^d 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; and a carbon number 1 such as a methoxycarbonyl group or an ethoxycarbonyl group To 10 alkoxycarbonyl and the like.

Among the compounds (IA), among R ¹ to R ⁸ , R ¹ to R ^{4 are} particularly preferably a hydrogen atom. R ⁵ to R ⁸ are each independently preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbons which may have a substituent, or an alkoxy group having 1 to 20 carbons which may have a substituent, more preferably It is a hydrogen atom or a hydroxyl group.

In the compound (IA), two to four of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are each independently preferably a hydroxyl 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 is preferably saturated. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic, and is preferably linear or branched.

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

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

The methylene group contained in the aforementioned aliphatic hydrocarbon group having 1 to 20 carbon atoms may be replaced with -O-. Examples of the group in which the methylene group contained in the aliphatic hydrocarbon group is replaced with -O- include a group represented by the following formula. In the following formula, * represents a bonding end.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, stubyl, trimethylphenyl, dipropylphenyl, bis (2,2-dimethylpropyl) phenyl, naphthyl, and the like. . The carbon number of the aforementioned aromatic hydrocarbon group is preferably from 6 to 16, more preferably from 6 to 12, and even more preferably from 6 to 9.

R ^9A to R ^12A represents the carbon number of the hydrocarbon group of 1 to 20 may have a substituent group, examples of the substituent include: -CO ₂ ^-; a carboxyl _{^{group; -SO 3 -; -CONZ 1 Z}} 2 (Z 1 and Z ² each independently represents a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms which may have a substituent; a halogen atom such as a fluorine atom, a chlorine atom, or iodine; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group Hydroxyl groups; sulfamoyl groups; alkoxycarbonyl groups having 1 to 10 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl groups;

Examples of the substituent -CONZ ¹ Z ² as 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. The aliphatic hydrocarbon group having 1 to 10 carbon atoms may be any of linear, branched, and cyclic.

As specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms, the number of carbon atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A is 1 to 10 By.

In the substituent -CONZ ¹ Z ² , a hydrocarbon group having 1 to 10 carbon atoms represented by Z ¹ and Z ² may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and iodine; and a methoxy group. Alkoxy groups having 1 to 10 carbons such as alkyl, ethoxy, etc .; hydroxyl groups; sulfamoyl groups; alkoxycarbonyl groups having 1 to 10 carbons such as methoxycarbonyl and ethoxycarbonyl.

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. Having the -CO ₂ ^- as a substituent hydrocarbon group having a carbon number of 1 to 20 preferably has the ideal line 1-2 -CO ₂ ^-, more preferably having 1 -CO ₂ ^-. The -CO ₂ ^- is preferably bonded to at least a terminal of a hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent. Examples of such a hydrocarbon group having 1 to 20 carbon atoms having -CO ₂ ^- as a substituent include a group represented by the following formula. In the following formula, * represents a bonding end.

At least one of R ^9A to R ^12A is preferably 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 a substituent is preferably a phenyl group, a trimethyl group, a trimethylphenyl group, a dipropylphenyl group, or a bis (2,2-dimethylpropyl) group. Phenyl, more preferably 2,4-dimethylphenyl or 2,4,6-trimethylphenyl.

In the compound (IA), it is preferable that 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 are each independently a substituent that may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms.

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

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

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

In addition, bA is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1 bA.

In the case where the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A does not have -SO ₃ ^- as a substituent, kA refers to the total of -CO ₂ ^- contained in formula (IA), and is preferably It is 1 to 5, more preferably 2 to 4, and even more preferably 2.

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

The compound (IA) is preferably a compound represented by formula (IA-1) to formula (IA-54), more preferably a compound represented by formula (IA-1) to formula (IA-18), and particularly preferably a formula Compounds represented by (IA-1) to formula (IA-3).

[Table 1]

[Table 2]

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

In Tables 1 to 2, ca1 to ca6 represent a group represented by the following formula (* means a bonding end).

"Compound (IB)"

A compound represented by the formula (IB).



[In formula (IB),
R ¹ to R ^{8 have the} same meanings as above;
R ^9B to R ^12B each independently represent a hydrocarbon group having 1 to 20 carbons which may have a substituent, and at least one of R ^9B to R ^12B is an aliphatic having 1 to 20 carbons having -SO ₃ ^- as a substituent Hydrocarbyl
QB ^{n +} represents a hydrogen positive ion or an n-valent metal ion;
n represents an integer of 2 or more;
bB represents the number of QB ^{n +} ;
When the total number of -SO ₃ ^- contained in R ¹ to R ⁸ and R ^9B to R ^12B is set to kB, aB is (n × bB) / kB]

Among the compounds (IB), among R ¹ to R ⁸ , R ¹ to R ^{4 are} particularly preferably a hydrogen atom. R ⁵ to R ⁸ are each independently preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbons which may have a substituent, or an alkoxy group having 1 to 20 carbons which may have a substituent, more preferably It is a hydrogen atom or a hydroxyl group.

In the compound (IB), preferably 2 to 4 of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are each independently a hydroxyl group. In particular, in terms of good heat resistance and light resistance, it is preferable that R ⁵ and R ⁸ are hydroxyl groups, and R ⁶ and R ⁷ are hydrogen atoms.

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

R ^9B to R ^12B represents the carbon number of the hydrocarbon group of 1 to 20 may have a substituent group, examples of the substituent include: -SO ₃ ^-; fluorine atom, a chlorine atom, a halogen atom such as iodine; methoxy, ethoxy Alkoxy groups having 1 to 10 carbons; hydroxy; amine sulfonyl; alkoxycarbonyl groups having 1 to 10 carbons such as methoxycarbonyl and ethoxycarbonyl.

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. Having the -SO ₃ ^- carbon atoms as a substituent of an aliphatic hydrocarbon group of 1 to 20 over the line preferably has 1-2 more -SO ₃ ^-, more preferably having a -SO ₃ ^-. The -SO ₃ ^- is preferably bonded to at least a terminal of an aliphatic hydrocarbon group having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent. Examples of such an aliphatic hydrocarbon group having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent include a group represented by the following formula. In the following formula, * represents a bonding end.

At least one of R ^9B to R ^12B is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. As the aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, a phenyl group, a stubyl group, a trimethylphenyl group, a dipropylphenyl group or bis (2,2-dimethylpropyl) is preferred. Phenyl, more preferably 2,4-dimethylphenyl or 2,4,6-trimethylphenyl.

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

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 hydrogen positive ion, an alkaline earth metal ion or a typical metal ion, and more preferably a hydrogen positive ion, a barium ion, a magnesium ion, or an aluminum ion. From the viewpoints of heat resistance and light resistance, hydrogen cations, barium ions, or aluminum ions are preferred.

When QB ^{n +} is a hydrogen ion, the hydrogen ion system is present together with -SO ₃ ^- as -SO ₃ H.

The preferred range of n is the same as described above.

The compound (IB) is electrically neutral. When the total number of -SO ₃ ^- contained in R ¹ to R ⁸ and R ^9B to R ^12B is set to kB, aB is (n × bB) / kB.

In addition, bB is preferably 1 to 3, more preferably 1 to 2 and even more preferably 1 bB.

In addition, kB is preferably from 1 to 5, more preferably from 2 to 4, and even more preferably from 2.

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

The compound (IB) is preferably a formula (IB-1) to (IB-54), a formula (IB-109) to a formula (IB-162), a formula (IB-217) to a formula (IB-270), a formula (IB-325) to compounds represented by formula (IB-378),
More preferably, the formulas (IB-37) to (IB-54), (IB-145) to (IB-162), (IB-253) to (IB-270), and (IB-361) ) To the compound represented by formula (IB-378),
Especially preferred are formula (IB-37) to formula (IB-39), formula (IB-145) to formula (IB-147), formula (IB-253) to formula (IB-255), formula (IB-361 ) To compounds represented by formula (IB-363).

[table 3]

[Table 4]

[table 5]

[TABLE 6]

[TABLE 7]

[TABLE 8]

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

In Tables 3 to 8, su1 to su6 represent groups represented by the following formula (* means a bonding end).

"Compound (IC)"

A compound represented by formula (IC).


[In formula (IC),
R ¹ to R ^{8 have the} same meanings as above;
R ^9C to R ^12C each independently represent a hydrocarbon group having 1 to 20 carbons which may have a substituent, and at least one of R ^9C to R ^12C is a hydrocarbon group having 1 to 20 carbons having -CONZ ¹ Z ² as a substituent 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;
Z ¹ and Z ² each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom which may have a substituent. ]

Among the compounds (IC), R ¹ to R ⁸ and R ¹ to R ^{4 are} particularly preferably a hydrogen atom. R ⁵ to R ⁸ are each independently preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbons which may have a substituent, or an alkoxy group having 1 to 20 carbons which may have a substituent, more preferably It is a hydrogen atom or a hydroxyl group.

In the compound (IC), preferably 2 to 4 of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are each independently a hydroxyl group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9C to R ^12C are the same as the hydrocarbon group having 1 to 20 carbon atoms represented by R ^9A to R ^12A , and the preferred carbon number ranges are also the same.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^9C to R ^12C may have a substituent. Examples of the substituent include: -CONZ ¹ Z ² ; a halogen atom such as a fluorine atom, a chlorine atom, and iodine; a methoxy group, an ethoxy group Alkoxy groups having 1 to 10 carbon atoms; hydroxyl groups; sulfamoyl groups; alkoxycarbonyl groups having 1 to 10 carbon groups such as methoxycarbonyl and ethoxycarbonyl groups.

Z ¹ and Z ^{2 have the} same meanings as described above.

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

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. The aforementioned hydrocarbon group having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent preferably has 1 to 2 -CONZ ¹ Z ² and more preferably 1 -CONZ ¹ Z ² . The -CONZ ¹ Z ² is preferably bonded to at least the terminal of a hydrocarbon group having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent. Examples of such a hydrocarbon group having 1 to 20 carbon atoms having -CONZ ¹ Z ² as a substituent include a group represented by the following formula. In the following formula, * represents a bonding end.

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. As the aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, a phenyl group, a stubyl group, a trimethylphenyl group, a dipropylphenyl group or bis (2,2-dimethylpropyl) is preferred. Phenyl, more preferably 2,4-dimethylphenyl or 2,4,6-trimethylphenyl.

In the compound (IC), it is preferable that 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 are each independently optionally substituted. An aromatic hydrocarbon group having 6 to 20 carbon atoms.

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

The compound (IC) is preferably a compound represented by formula (IC-1) to formula (IC-54), more preferably a compound represented by formula (IC-1) to formula (IC-18), and particularly preferably a formula (IC-1) to the compound represented by Formula (IC-3).

[TABLE 9]

[TABLE 10]

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

In Tables 9 to 10, bm1 to bm6 represent a group represented by the following formula (* means a bonding end).

The compound represented by formula (IA) and the case where Q ^{n +} = n-valent metal ion is represented by formula (IB) is equivalent to the compound represented by formula (pt5) in the following chemical formula. The compound represented by formula (IB) and the compound represented by formula (IC) in the case where Q ^{n +} = hydrogen positive ion are equivalent to the compound represented by formula (pt4) in the following chemical 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) can be obtained by combining the compound represented by formula (pt4) with a halide (preferably chloride) containing an n-valent metal ion, acetate, phosphate, sulfate, silicate Or it is produced by reacting cyanide and the like.

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



[In formulae (pt1) to (pt2) and (pt4) to (pt5), R ¹ to R ⁸ are the same as above; R ^9X to R ^12X represent R ^9A to R ^12A and R ^9B to R ^12B , Or R ^9C to R ^12C ; QX ^{n +} means QA ^{n +} , QB ^{n +} , or QC ^{n +} ; aX means aA, aB, or aC; bX means bA, bB, or bC; 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 described above, and R ^9aX to R ^12aX each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent]

<Colored resin composition>

The colored resin composition of the present invention includes a colorant (A) and a resin (B), and the colorant (A) includes a compound represented by Formula (IA), a compound represented by Formula (IB), and a compound represented by Formula (IC) At least one selected from the group consisting of the indicated compounds.

The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

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

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

<Colorant (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 a colorant (A). The content of the compound (IA), the compound (IB), and / or the compound (IC) is preferably 0.1 to 150 parts by mass, and more preferably 0.5 to 100 parts by mass based on 100 parts by mass of the resin (B). Parts, particularly preferably 1 to 80 parts by mass.

In the total amount of the colorant (A), the total content 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, particularly preferably 90% by mass or more.

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

The dye (A1) is not particularly limited, and conventional dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. As the dye, for example, a compound classified as a substance having a hue other than a pigment in the Colour Index (published by The Society of Dyers and Colourists) or a coloring note ( The dyes known in the dyeing company). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, Methylene dye, azomethine dye, squarylium dye (except compound (IA), compound (IB), and compound (IC)), acridine dye, styryl dye, fragrance Legumin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and conventional pigments can be used, and examples thereof include pigments classified as pigments in the Dye Index (published by the British Society of Dyestuffs and Colorants).

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments;
CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
CI pigment purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments;
CI Pigment Green 7, 36, 58 and other green pigments;
CI pigment brown 23, 25 and other brown pigments;
CI Pigment Black 1, 7 and other black pigments.

The content of the colorant (A) is preferably from 0.1% by mass to 70% by mass, more preferably from 0.5% by mass to 60% by mass, and even more preferably from 1% by mass to 5% of the total solid content of the colored resin composition. 50% by mass.

Here, the "total amount of solid content" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored resin composition. The total amount of the solid components and the content of the respective components opposed thereto can be measured by a known analytical method such as liquid chromatography or gas chromatography.

＜ Resin (B) ＞

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

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono [2- ( Methacrylfluorenyloxyethyl] ester and the like are preferably acrylic acid, methacrylic acid, and maleic anhydride.

(B) It is preferably a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxygen ring, and a tetrahydrofuran ring) and (methyl) Acrylic fluorenyloxy monomer.

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

Examples of (b) include glycidyl (meth) acrylate, vinyl benzyl glycidyl ether, and 3-, 4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl Esters, 3-ethyl-3- (meth) acrylfluorenyloxymethyloxyphosphonium, tetrahydrofurfuryl (meth) acrylate, etc .; preferably glycidyl (meth) acrylate, (meth) Acrylic-3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester, 3-ethyl-3- (meth) acrylfluorenyloxymethyloxyfluorene.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and (methyl) ) Tricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N -Cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene, and the like, preferably styrene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are suitable.

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

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

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

In terms of solid content, the acid value of the resin (B) is preferably 20 mg-KOH / g (mg-KOH / g) to 170 mg-KOH / g, and more preferably 30 mg-KOH / g to 150 mg-KOH / g, particularly preferably from 40 mg-KOH / g to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 gram of the resin (B), and can be obtained by, for example, titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 30% to 99.9% by mass, more preferably 50% to 99.5% by mass, and even more preferably 70% to 99% by mass relative to the total solid content of the colored resin composition. quality%.

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

<Polymerizable compound (C)>

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dioxin Pentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, etc.

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

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

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, and the like by the action of light or heat and starts polymerization, and a conventional polymerization initiator can be used. Examples of the polymerization initiator that generates living radicals include N-benzyloxy-1- (4-phenylhydrothiophenyl) butane-1-one-2-imine, and N- Benzamyloxy-1- (4-phenylhydrothiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylhydrothiophenyl) Group) -3-cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- (4-phenylhydrothiophenyl) -3-cyclohexylpropane-1-one- 2-imine, 2-methyl-2-morpholinyl-1- (4-methylhydrothiophenyl) propane-1-one, 2-dimethylamino-1- (4-? Folinylphenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5- Triazine, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl Biimidazole and others.

When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably from 0.1 parts by mass to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 30 parts by mass, more preferably 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the aforementioned range, there is a tendency that the sensitivity is increased and the exposure time is shortened, so the productivity of the color filter is improved.

＜ Polymerization starter (D1) ＞

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiator (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) ) Benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl thioxanthone, N-phenylglycine, etc.

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

＜ Solvent (E) ＞

The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include: ester solvents (solvents containing -COO- and -O- free), ether solvents (solvents containing -O- and -COO- free), and ether ester solvents (containing- COO- and -O- solvents), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (molecules containing OH and no -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene and the like.

Examples of the solvent include:
Ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, ethyl acetate, cyclohexanol acetate, and Ester solvents such as γ-butyrolactone (solvents containing -COO- and no -O- in the molecule);
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 ether ( Solvents containing -O- and -COO- in the molecule);
Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Ether ester solvents such as alcohol monoethyl ether acetate (solvents containing -COO- and -O- in the molecule);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptone, 4-methyl-2-pentanone, cyclohexanone (including -CO- in the molecule and -COO-free) -Solvent);
Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-);
Solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

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. ester.

In the case where the solvent (E) is contained, the content of the solvent (E) is preferably 60% to 95% by mass, and more preferably 65% to 92% by mass relative 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, and 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 coating becomes good, and when the color filter is formed, the color density is not insufficient, and therefore the display characteristics tend to be good.

＜ Leveling agent (F) ＞

Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group on a side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specific examples are: TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (trade names: manufactured by Toray Dow Corning Corporation); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Acto Advanced Materials Japan Contracts) Wait.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples: FLUORAD (registered trademark) FC430, FLUORAD FC431 (made by Sumitomo 3M Co., Ltd.); MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation); EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronics & Chemical Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (made by Asahi Glass Co., Ltd.); and E5844 (made by Daikin Fine Chemical Research Institute Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

In the case where the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001% by mass to 0.2% by mass, and more preferably 0.002% by mass to 0.1% by mass relative to the total amount of the colored resin composition. %. In addition, the content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be made good.

＜ Other ingredients ＞

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

<Manufacturing method of colored resin composition>

The colored resin composition of the present invention can be obtained by using a colorant (A) and a resin (B), and a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiator (D1), if necessary. , Solvent (E), leveling agent (F) and other ingredients.

＜ Manufacturing method of color filter ＞

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

The colored resin composition can be prepared by including 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 with excellent heat resistance. This color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL (electroluminescence) device, an electronic paper, etc.) and a solid-state imaging element.

[Example]

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

Hereinafter, the structure of the compound is confirmed by mass spectrometry (LC, Model 1200 manufactured by Agilent; Agilent, LC / MSD model manufactured by Agilent).

(Synthesis example 1)

100 parts of 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 55 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 51 parts Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 1.5 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.3 parts of bis (tri-tertiary butyl phosphine) palladium (Ao 100 parts of water and 1,000 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) were mixed, and heated at 90 ° C with stirring for 1 hour. After completion of the reaction, the organic layer was separated with water and ethyl acetate to separate the organic layer. Then, the organic layer was dried with magnesium sulfate, and the solvent was distilled off with an evaporator to obtain 113 parts of a compound represented by the formula (1A-1).
Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 258.2
Exact Mass: +257.1

(Synthesis example 2)

70 parts of the compound represented by the formula (1A-1), 53 parts of 4-chloro-4-p-oxybutyric acid methyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) and 700 parts of toluene (Kanto Chemical Co., Ltd. (Manufactured by the company), mixed and heated at 100 ° C for 16 hours while stirring. After the reaction, the solvent was distilled off. 700 parts of hexane (manufactured by Kanto Chemical Co., Ltd.) was added to the obtained crude product, and the mixture was stirred for 2 hours, and the solid was separated by filtration to obtain 90 parts of the formula (1A- 2) The compound indicated.
Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 372.2
Exact Mass: +371.1

(Synthesis example 3)

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

(Synthesis example 4)

89 parts of the crude product A was 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 Industry Co., Ltd.) was added. Stir at room temperature at 23 ° C for 16 hours. After the reaction is completed, water is added and the solvent is distilled off. The obtained crude product is separated and purified by silica gel column chromatography to obtain 53 parts of the formula (1A-3). The indicated compound.
Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 344.2
Exact Mass: +343.1

(Synthesis example 5)

53 parts of the compound represented by the formula (1A-3) was dissolved in 530 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0 ° C, 460 parts of a borane 1M tetrahydrofuran solution (Kanto Chemical) was added dropwise. Co., Ltd.). After the dropwise addition was completed, the mixture was stirred at 20 ° C for 5 hours. After the reaction, water was added, and the solvent was distilled off. The obtained crude product was separated and purified by column chromatography to obtain 25 parts of the compound represented by the formula (1A-4).
Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 330.3
Exact Mass: +329.2

Add 4 parts of the compound represented by formula (1A-4), 2.5 parts of lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 20 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), and 20 parts Tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) was stirred at room temperature of 23 ° C for 5 hours. After 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 the 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 the formula (1A-5) and 0.3 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 65 parts. Part of toluene (manufactured by Kanto Chemical Co., Ltd.) and 17 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated under stirring at 120 ° C for 2 hours. After the reaction, the solvent was distilled off, and the obtained crude product 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 spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 709.3
Exact Mass: +708.3

[Example 1]

1.0 part of the compound represented by the formula (1A-6) was added to 25 parts of a 0.8% aqueous sodium hydroxide solution to dissolve it to prepare an aqueous solution 1. In addition, 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 gradually added to room temperature at 23 ° C. After being in the aqueous solution 1, it was stirred for 30 minutes. After completion of the reaction, the solid obtained by suction filtration was 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 the 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-butanesultone (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in a nitrogen atmosphere. Among 5.0 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), the mixture was heated at 100 ° C for 3 hours while being stirred. After the reaction was completed, toluene was distilled off by an evaporator, and then 50 parts of a 10% sodium hydroxide aqueous solution was added to precipitate a solid. After the solid was obtained by suction filtration, the solid was rinsed and washed with water and hexane. It was dried under reduced pressure at 60 ° C. for 12 hours to obtain 20.0 parts of a compound represented by the formula (1B-1). 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), 10.0 parts of 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry), and 0.3 parts of palladium acetate (Tokyo Chemical Industry Co., Ltd.) (Manufactured), 0.47 parts of tertiary-tertiary butylphosphine 1.0M hexane solution (Wako Pure Chemical Industries, Ltd.) was dissolved in 200 parts of toluene (Tokyo Chemical Industry Co., Ltd.), under nitrogen atmosphere at room temperature Stir for 10 minutes. To this was added 9.0 parts of sodium tertiary butoxylate (Tokyo Chemical Industry Co., Ltd.), and the mixture was heated at 110 ° C for 4 hours while stirring. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and then separated with water and ethyl acetate to separate an organic layer. Then, the organic layer was dried with magnesium sulfate, and ethyl acetate was distilled off with an evaporator to obtain 6.1 parts of a compound represented by the formula (1B-2). 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 the formula (1B-2) was 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.) in a nitrogen atmosphere. And stirred at 50 ° C for 5 hours. After the reaction was completed, acetic acid and hydrobromic acid were distilled off by an evaporator. After separating the organic layer 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 the formula (1B-3) and 1.0 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 70 Part of 1-butanol (manufactured by Kanto Chemical Co., Ltd.) and 49 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) were stirred at 110 ° C. for 3 hours. After the reaction was completed, 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 the formula (1B-4). The yield was 27%.



Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 809.2
Exact Mass: +808.23

[Example 3]

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

[Example 4]

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

(Synthesis example 10)

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 in Synthesis Example 8, 9.9 parts of the compound represented by the formula (1B-7) was obtained. The yield was 52%.



Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 350.5
Exact Mass: 349.13

[Example 5]

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



Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 777.5
Exact Mass: +776.2

[Example 6]

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

[Example 7]

In the same manner as in Example 6, except that 2.3 parts of aluminum sulfate fourteen to eighteen hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were used instead of barium chloride dihydrate in Example 6. 0.7 part of the compound represented by the formula (1B-10). The yield was 52%.

[Example 8]

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 in Example 6, 0.3 parts of the formula (1B-11 ). The yield was 22%.

(Synthesis example 11)

20.0 parts of 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 11.2 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10.3 parts Potassium hydroxide, 0.47 parts of bis (tri-tert-butylphosphine) palladium (0), and 0.30 parts of tetrabutylammonium bromide dissolved in 200 parts of toluene under a nitrogen atmosphere (manufactured by Kanto Chemical Co., Ltd. ) And 20 parts of water, stir at 90 ° C for 16 hours while stirring. After completion of the reaction, the organic solvent was distilled off with an evaporator to obtain 25 parts of a compound represented by the formula (1C-1).
Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 258.2
Exact Mass: +257.1

(Synthesis example 12)

25 parts of the compound represented by the formula (1C-1) and 19.0 parts of monomethyl succinate monochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 250 parts of toluene under a nitrogen atmosphere (Kanto Chemical Co., Ltd. (Manufactured by the company), heated at 100 ° C for 16 hours while stirring. After the reaction was completed, water was added to separate the organic layer, and the organic layer was concentrated by an evaporator, and then separated and purified by silica gel column chromatography to obtain 22 parts of a compound represented by the formula (1C-2).
Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 372.2
Exact Mass: +371.2

(Synthesis example 13)

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

(Synthesis example 14)

23 parts of crude product B was added to 200 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) under a nitrogen atmosphere, cooled to 0 ° C, and 18 parts of thionyl chloride was added dropwise. After the dropwise addition was completed, the temperature was raised to room temperature, and the mixture was stirred for 5 hours. After the reaction was completed, water was added to separate the organic layer. It was dried with magnesium sulfate, the solvent was distilled off with an evaporator, and the silica gel column chromatography was used for separation and purification to obtain 16 parts of the compound represented by the formula (1C-3).

(Synthesis Example 15)

16.0 parts of the compound represented by the formula (1C-3) was dissolved in 160 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) under a nitrogen atmosphere, and after cooling to 0 ° C, 140 parts of borane 1M tetrahydrofuran was added dropwise. Solution (manufactured by Tokyo Chemical Industry Co., Ltd.). After completion of the dropwise addition, the temperature was raised to 20 ° C, and the mixture was stirred for 5 hours. After adding water, the organic layer was separated, concentrated with magnesium sulfate, and the solvent was distilled off with an evaporator. The silica gel column chromatography was used for separation and purification to obtain 6 parts of the compound represented by the formula (1C-4).
Identification: (Mass spectrum) Ionization mode = ESI +: m / z = [M + H] ⁺ 330.3
Exact Mass: +329.2

(Synthesis Example 16)

Dissolve 5 parts of the compound represented by the formula (1C-4) in 5 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), add 20 parts of ammonia 4M methanol solution, and place in an autoclave at 60 ° C next Heat with stirring for 48 hours. After the reaction was completed, the solvent was concentrated by 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 the formula (1C-5) and 0.5 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a nitrogen atmosphere. It was dissolved in 20 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 5 parts of 1-butanol (manufactured by Kanto Chemical Co., Ltd.), and heated at 120 ° C while stirring. After the reaction, the solvent was distilled off with an evaporator, 40 parts of tetrahydrofuran was added, and the mixture was stirred for 1 hour, followed by filtration and drying, thereby obtaining 2.4 parts of the compound represented by the formula (1C-6).
Identification: (Mass spectrum) 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 funnel, and a stirrer, an appropriate amount of nitrogen was flowed to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added, and heated to 85 ° C while stirring. Next, the following mixed solution was added dropwise over 4 hours: 54 parts of acrylic acid, 225 parts of acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-yl ester, and acrylic acid 3,4- Epoxy tricyclo [5.2.1.0 ^2,6 ] dec-9-yl ester mixture (mixing ratio of 1: 1), 81 parts of vinyl toluene (isomer mixture), 80 parts of propylene glycol monomethyl ether Acetate. On the other hand, it took 5 hours to dropwise add 30 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) to 160 parts of propylene glycol monomethyl ether acetate. The solution. After the dropwise addition of the starter solution was completed, the flask was kept at 85 ° C for 4 hours, and then cooled to room temperature to obtain a type B viscosity (23 ° C) of 246 mPa. Copolymer (resin (B-1)) solution with a solid content of 37.5% in seconds (mPa · s). The weight average molecular weight Mw of the resulting copolymer was 10600, the degree of dispersion was 2.01, and the acid value of the solid content was 115 mg-KOH / g. The resin (B-1) has the following structural units.

(Resin Synthesis Example 2)

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed and replaced with a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was added, and heated to 80 ° C while stirring. Then, the following mixed solution was added dropwise over 5 hours: 38 parts of acrylic acid, 289 parts of acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-yl ester, and acrylic acid 3,4- Epoxy tricyclo [5.2.1.0 ^2,6 ] dec-9-yl ester mixture (mixing ratio of 1: 1), 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition was completed, the inside of the flask was held at 80 ° C for 4 hours, and then cooled to room temperature to obtain a type B viscosity (23 ° C) of 125 mPa. Copolymer (resin (B-2)) solution with a solid content of 35.1% in seconds. The weight average molecular weight Mw of the resulting copolymer was 9200, the degree of dispersion was 2.08, and the acid value of the solid content was 77 mg-KOH / g. The resin (B-2) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by a GPC (gel permeation chromatography) method under the following conditions.
Device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min (mL / min)
Test solution solid content concentration: 0.001% by mass to 0.01% by mass
Injection volume: 50 microliters (μL)
Detector: RI
Calibration reference material: TSK STANDARD POLYSTYRENE (standard polystyrene)
F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

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 bis Acetone alcohol was mixed, 300 parts of zirconia beads with a diameter of 0.2 micrometers were placed therein, and a paint conditioner (manufactured by LAU) was used to shake for 3 hours, and the zirconia beads were removed to prepare a dispersion (P-1) .

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

[TABLE 11]

In Table 11, each component shows the following compounds.
Colorant (A-1): Compound represented by formula (1A-7) Colorant (A-2): Compound represented by formula (1B-4) Colorant (A-3): Formula (1B-5) Compound colorant (A-4): compound colorant (A-5) represented by formula (1B-6): compound colorant (A-6) represented by formula (1B-8): formula ( Compound colorant (A-7) represented by 1B-9): Compound colorant (A-8) represented by formula (1B-10): Compound colorant (A-9) represented by formula (1B-11) ): Compound resin (B-1) represented by formula (1C-6): 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 a composition shown in Table 12, and the coloring resin composition was obtained.

[TABLE 12]

In Table 12, each component shows the following compounds.
Colorant (AX): 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 "TORAY SILICONE SH8400" manufactured by Co., Ltd.)

＜ Production of color filter (color coating film) 1 ＞

A colored resin composition was applied on a 5 cm square glass substrate (Eagle 2000, manufactured by Corning) by a spin coating method, and then pre-baked at 100 ° C for 3 minutes to obtain a colored coating film.

＜ Measurement of chromaticity ＞

The chromaticity of the colored coating film is based on the spectrophotometer and the characteristic function of the C light source measured using a colorimeter (OSP-SP-200, manufactured by Olympus Co., Ltd.) as xy in the XYZ color system of CIE The chromaticity coordinates (x, y) and the stimulus value Y were obtained.

＜ Evaluation of heat resistance ＞

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

[TABLE 13]

[Examples 19 to 25]

[Preparation of colored resin composition]

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

[TABLE 14]

In Table 14, each component shows the following compounds.
Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D-1): N-ethoxyl-1- (4-phenylhydrothiophenyl) -3-cyclohexylpropane-1-one-2-imine (PBG-327, Oxime compound, manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.)
Other symbols are the same as those described above.

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

The colored resin composition was applied on a 5 cm square glass substrate (Eagle 2000, manufactured by Corning) using a spin coating method, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After leaving to cool, the coloring composition layer formed on the substrate was exposed to 100 millijoules per square centimeter (mJ / cm ² ) using an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.) in an atmospheric environment using an exposure machine. The exposure amount (based on 365 nanometers) was irradiated with light. After light irradiation, post-bake at 230 ° C. for 30 minutes in an oven to obtain a colored coating film.

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

[Table 15]

[Industrial availability]

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

no

no

Claims (5)

A compound represented by formula (IA), formula (IB), or formula (IC): In formula (IA), R ¹ to R ⁸ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbons which may have a substituent, and an alkoxy group having 1 to 20 carbons which may have a substituent; R ^9A to R ^12A each independently represent a hydrocarbon group having 1 to 20 carbons which may have a substituent, and at least one of R ^9A to R ^12A is a hydrocarbon group having 1 to 20 carbons having -CO ₂ ^- as a substituent; QA ^{n +} represents an n-valent metal ion; n represents an integer of 2 or more; bA represents the number of QA ^{n +} ; the total of the negative charges contained in R ¹ to R ⁸ and R ^9A to R ^12A is set to kA When aA is (n × bA) / kA, In formula (IB), R ¹ to R ⁸ represent the same meanings 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 It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms having -SO ₃ ^- as a substituent; QB ^{n +} represents a hydrogen ion or an n-valent metal ion; n represents an integer of 2 or more; bB represents the number of QB ^{n +} ; When the total number 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 meanings as above; R ^9C to R ^12C each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R ^9C to R ^12C It is a hydrocarbon group having 1 to 20 carbons having -CONZ ¹ Z ² as a substituent, and at least one of R ^9C to R ^12C is an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent; Z ¹ and Z ² each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom which may have a substituent. A colored resin composition comprising a colorant and a resin, wherein the colorant includes a compound represented by formula (IA) as described in claim 1, a compound represented by formula (IB), and a compound represented by formula (IC) At least one selected from the group consisting of the indicated compounds. The colored resin composition according to claim 2, further 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 includes the color filter according to claim 4.