JP7158868B2 - Coloring composition containing complex compound, colorant for color filter, and color filter - Google Patents

Description

The present invention relates to a complex compound of an azo dye and a metal, a coloring composition containing the complex compound, a colorant for color filters using the coloring composition, and a color filter using the colorant.

Color filters are sometimes used in liquid crystal and electroluminescence (EL) display devices. A color filter is produced by laminating a colored layer on a translucent substrate such as glass by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. Colorants used in the colored layer are broadly classified into pigments and dyes, and pigments, which are generally considered to be excellent in heat resistance and light resistance, are widely used (see, for example, Patent Documents 1 to 3). However, pigments are generally insoluble in solvents and exist in the form of fine particles in color filters containing resins. It is known that the reflection and scattering affect the transparency and color purity, and that the contrast ratio of the color liquid crystal display device is lowered due to the depolarization effect caused by the reflection.

In order to solve the problem of the decrease in contrast ratio, a method using only a dye as a coloring agent or a method using both a dye and a pigment has been proposed. Since dyes are soluble in solvents, color filters using dyes have less depolarization and superior spectral characteristics compared to the case where only pigments are used as colorants. Xanthene dyes and the like are known as dyes used in color filters because of their excellent color development, heat resistance and light resistance (see, for example, Patent Documents 4 to 8). The C.I. I. Acid Red 289 and C.I. I. It is disclosed that xanthene-based dyes such as Acid Red 52 are used in combination with azopyridone-based dyes to provide excellent red hues. Here, C.I. I. means color index.

Further, it is known that a blue color filter with high contrast ratio and color purity can be produced by using these xanthene dyes or derivatives thereof together with phthalocyanine dyes (see, for example, Patent Documents 6 and 7). In such a color filter using both dyes and pigments, agglomerates of different colors are mixed to form aggregates, and charge transfer immediately occurs between the photoexcited dye molecules and nearby pigment molecules, resulting in oxidation. It is thought that they also have the effect of mutually suppressing decomposition, and compared to a color filter produced by using a single dye, it is possible to maintain color development and improve light resistance.

Azo dyes, which are one type of dyes, are widely used as dyes because they come in a wide variety of colors, are easy to obtain raw materials, and are simple to manufacture. However, although conventional azo dyes can ensure a certain degree of solubility in alcohols such as water and methanol (Patent Document 9), they have poor solubility in organic solvents used in manufacturing color filters. sufficient, and further improvement in solubility is desired (Patent Document 10). In particular, azo dye complexes synthesized for the purpose of improving heat resistance and color development due to the effect of increasing the molecular weight and the effect of electronic stability are required to be improved because of their low solubility in organic solvents.

Cyanuric chloride is a compound used to improve the dispersibility of reactive dyes and pigments (Patent Documents 11 to 14). Patent Document 14 discloses a reaction product of an organic dye and sialic chloride, which aims to stably mix and disperse pigment particles in a vehicle, and mentions dissolution in the vehicle. It has not been. In other words, there is still no suggestion or disclosure from the viewpoint of dyeing the reaction product of an organic dye and sialic chloride.

Japanese Patent Application Laid-Open No. 2001-220520 Japanese Patent Publication No. 2007-533802 Japanese Unexamined Patent Application Publication No. 2012-12498 JP-A-2002-265834 JP 2012-207224 A JP 2010-254964 A JP 2014-12814 A JP 2014-59538 A Japanese Patent No. 3927001 JP 2013-040240 A Japanese Patent No. 4250777 Japanese Patent No. 4446339 JP 2017-197719 A Japanese Patent No. 5705754 JP-A-10-36692

The present invention provides a novel azo dye complex compound that has good solubility in organic solvents such as propylene glycol monomethyl ether (PGME), which is commonly used in the production of color filters, and also has excellent heat resistance. intended to provide

Further, a coloring composition containing a novel azo dye complex compound having a solid (powder, etc.) state necessary for exhibiting good solubility or dispersibility in the manufacturing process of a color filter, and the coloring composition It is an object of the present invention to provide a colorant for a color filter, and a color filter using the colorant for a color filter, which is excellent in color developability (color gamut, brightness, contrast ratio, etc.).

As a result of intensive studies to solve the above problems, the present inventors have found that a complex compound of an azo dye and a metal is resistant to organic solvents such as PGME while maintaining heat resistance as a dye with superior transparency to pigments. The inventors have found that good solubility can be imparted, and completed the present invention.

Furthermore, the present inventors incorporated a coloring composition containing a complex compound of an azo dye and a metal into a colorant for color filters, and studied color filters as a colorant for color filters, and completed the present invention. let me

That is, the present invention has the following gist obtained from the results of intensive research to achieve the above object.

The present invention is a complex compound of an azo dye and a metal represented by the following general formula (1).

（１）

(1)

In general formula (1), Ar1 and Ar2 are each independently
represents an optionally substituted aromatic hydrocarbon group or heteroaromatic ring group having 3 to 20 atoms consisting of one or more of carbon, nitrogen, oxygen and sulfur atoms;
R1 to R2 are each independently a hydrogen atom,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, or
It represents an optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms, and R1 and R2 may combine with each other to form a ring.
n and m are 1 or 2, and when n and m are 2, they may be different groups.
X1, X2, and X3 each independently represent an amino group, an ether group, a sulfonyl group, a sulfoxide group, an ester group, an amide group, a urea group, a thioether group, a thioester group, a thioamide group, a thiourea group, a urethane group, and a sulfonate ester. group, sulfonamide group and carbamoyl group.
M represents a positive metal ion. q represents an integer of 1 to 4;

The present invention also provides a complex compound in which M in the general formula (1) is nickel ion, zinc ion, cobalt ion, chromium ion, iron ion, copper ion, or aluminum ion.

The present invention is a complex compound wherein X1, X2 and X3 in the general formula (1) are each independently an amino group or an ether group.

The present invention provides a complex compound of an azo dye containing one of the heteroaromatic groups represented by the general formulas (2) to (8) and a metal in which Ar1 and Ar2 are each independently represented by the general formula (1). is.

（２）

(2)

（３）

(3)

（４）

(4)

（５）

(5)

（６）

(6)

（７）

(7)

（８）

(8)

In general formulas (2) to (8), R3 to R9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, —SO ₃ ⁻ ,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted cycloalkyl group having 3 to 20 carbon atoms,
an optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms,
an optionally substituted cycloalkoxy group having 3 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms,
an optionally substituted acyl group having 1 to 20 carbon atoms,
an optionally substituted amino group having 0 to 20 carbon atoms,
It represents an optionally substituted C6-C20 aromatic hydrocarbon group or an optionally substituted C2-C20 heterocyclic group.

Further, the present invention is the above complex compound in which the azo dye in the general formula (1) is an azo dye represented by the general formulas (9) to (11).

（９）

(9)

（１０）

(10)

（１１）

(11)

Among general formulas (9) to (11), R1, R2, n and m, X1, X2, and X3 are described in general formula (1) above.
R10 to R13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, —SO ₃ ⁻ ,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted cycloalkyl group having 3 to 20 carbon atoms,
an optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms,
an optionally substituted cycloalkoxy group having 3 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms,
an optionally substituted acyl group having 1 to 20 carbon atoms,
an optionally substituted amino group having 0 to 20 carbon atoms,
an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
or represents an optionally substituted heterocyclic group having 2 to 20 carbon atoms.
a is an integer of 1 to 4, b to d are integers of 1 to 6,
When a to d are 2 or more, each may be a different group.

Further, the present invention is the above-described complex compound having a solubility in propylene glycol monomethyl ether (PGME) at 25° C.±2° C. of 5% by weight or more when the powder is added to the solvent and the solubility is measured.

A coloring composition containing the present invention or the complex compound described above.

A colorant for a color filter containing the coloring composition of the present invention or the above.

A color filter using the present invention or the colorant for a color filter described above.

The complex compound of the azo dye and metal of the present invention has high solubility in organic solvents such as PGME and excellent heat resistance. Since it has a solid (powder, etc.) state necessary for exhibiting good solubility or dispersibility, it is suitable as a colorant for use in color filters. Therefore, the color filter obtained using the coloring agent is excellent in color development (color gamut, brightness, contrast ratio, etc.).

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

Complex compounds of azo dyes and metals represented by the general formula (1) include azo dyes represented by the following general formula (12). First, the azo dye represented by formula (12) will be described.

（１２）

(12)

In the general formula (12), Ar1 and Ar2 are each independently a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, which may have a substituent. Represents a hydrocarbon group and a heteroaromatic ring group. R1 and R2 each independently represents a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, and the number of carbon atoms which may be substituted. represents a cycloalkyl group of 3 to 20, or an optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms, wherein R1 and R2 are bonded to each other to form a ring; You may have n and m are 1 or 2; X1, X2, and X3 each independently represent an amino group, an ether group, a sulfonyl group, a sulfoxide group, an ester group, an amide group, a urea group, a thioether group, a thioester group, a thioamide group, a thiourea group, a urethane group, and a sulfonate ester. group, sulfonamide group and carbamoyl group.

In the general formula (12), represented by Ar1 and Ar2, "an aromatic having 3 to 20 atoms consisting of one or more of optionally substituted carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms Specific examples of the "substituent" in the "hydrocarbon group, heteroaromatic group" include a hydroxyl group, an amino group, an ether group, a sulfonyl group, a sulfoxide group, an ester group, an amide group, a urea group, a thioether group, a thioester group, Thioamide group; thiourea group, urethane group, sulfonate ester group, sulfonamide group, carbamoyl group; fluorine atom, chlorine atom, bromine atom, iodine atom and other halogen atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Cycloalkyl groups having 3 to 19 carbon atoms such as cyclooctyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc. straight-chain alkoxy group having 1 to 19 carbon atoms; branched alkoxy group having 3 to 19 carbon atoms such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group a cycloalkoxy group having 3 to 19 carbon atoms such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group and a cyclohexyloxy group; a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a triphenylenyl group Aromatic hydrocarbon groups or condensed polycyclic aromatic groups having 6 to 19 carbon atoms such as indenyl group and fluorenyl group; pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group , isoquinolyl group, naphthyridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group, furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, heterocyclic groups having 2 to 19 carbon atoms such as oxazolyl group, benzoxazolyl group, thiazolyl group and benzothiazolyl group; Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formula (12), represented by Ar1 and Ar2, "an aromatic having 3 to 20 atoms consisting of one or more of optionally substituted carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms Specific examples of the "aromatic hydrocarbon group or heteroaromatic ring group having 3 to 20 atoms consisting of one or more of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom" in the "hydrocarbon group or heteroaromatic ring group" include Specifically, aromatic hydrocarbon groups having 6 to 19 carbon atoms such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylenyl group, indenyl group and fluorenyl group; pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group, furanyl group, benzofuranyl group , a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a heteroaromatic ring group having 2 to 19 carbon atoms such as a benzothiazolyl group, and the like. can.

Specific examples of preferable compounds represented by Ar1 and Ar2 in the general formula (12) are shown in the following formulas (A-1) to (A-21), but the present invention is limited to these compounds. not a thing In the following structural formulas, some hydrogen atoms are omitted. In addition, even when stereoisomers exist, their planar structural formulas are described.

（Ａ－１）

(A-1)

（Ａ－２）

(A-2)

（Ａ－３）

(A-3)

（Ａ－４）

(A-4)

（Ａ－５）

(A-5)

（Ａ－６）

(A-6)

（Ａ－７）

(A-7)

（Ａ－８）

(A-8)

（Ａ－９）

(A-9)

（Ａ－１０）

(A-10)

（Ａ－１１）

(A-11)

（Ａ－１２）

(A-12)

（Ａ－１３）

(A-13)

（Ａ－１４）

(A-14)

（Ａ－１５）

(A-15)

（Ａ－１６）

(A-16)

（Ａ－１７）

(A-17)

（Ａ－１８）

(A-18)

（Ａ－１９）

(A-19)

（Ａ－２０）

(A-20)

（Ａ－２１）

(A-21)

In the general formula (12), in the "linear or branched alkyl group having 1 to 20 carbon atoms optionally having substituent(s)" represented by R1 and R2, "1 to 20 carbon atoms "linear or branched alkyl group" specifically includes linear groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Chain alkyl groups; branched alkyl groups such as isopropyl, isobutyl, s-butyl, t-butyl and isooctyl groups can be mentioned.

As the "cycloalkyl group having 3 to 20 carbon atoms" in the "optionally substituted cycloalkyl group having 3 to 20 carbon atoms" represented by R1 and R2 in the general formula (12) Specific examples include cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl groups.

In the general formula (12), in the "linear or branched alkenyl group optionally having 2 to 20 carbon atoms" represented by R1 and R2, "2 to 20 carbon atoms The linear or branched alkenyl group of" includes vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or a linear or branched alkenyl group in which a plurality of these alkenyl groups are bonded.

In the general formula (12), represented by R1 and R2, "a linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" or "a Specific examples of the "substituent" in the "linear or branched alkenyl group" include halogen atoms such as a fluorine atom, a chlorine atom _, a bromine atom and an iodine atom ^; Cycloalkyl groups having 3 to 19 carbon atoms such as cyclopentyl, cyclohexyl and cyclooctyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, linear alkoxy groups with 1 to 19 carbon atoms such as nonyloxy group and decyloxy group; A branched alkoxy group; a cycloalkoxy group having 3 to 19 carbon atoms such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group; a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, Aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 19 carbon atoms such as pyrenyl group, triphenylenyl group, indenyl group, fluorenyl group; pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group , triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group, furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl heterocyclic groups having 2 to 19 carbon atoms such as dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group and benzothiazolyl group. Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formula (12), the "substituent" in the "substituted cycloalkyl group having 3 to 20 carbon atoms" represented by R1 and R2 specifically includes a fluorine atom, a chlorine atom, and a bromine Atom, halogen atom such as iodine atom; —SO ₃ ⁻ ; C1 to C atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. 14 linear alkyl groups; branched alkyl groups having 3 to 14 carbon atoms such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group;
Cycloalkyl groups having 3 to 14 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyl linear alkoxy groups having 1 to 14 carbon atoms such as oxy group, octyloxy group, nonyloxy group, decyloxy group; isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group, etc. a branched alkoxy group having 3 to 14 carbon atoms; a cycloalkoxy group having 3 to 14 carbon atoms such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group; a vinyl group, a 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or a straight chain having 2 to 14 carbon atoms in which a plurality of these alkenyl groups are bonded or branched alkenyl group; aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 14 carbon atoms such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, indenyl group and fluorenyl group; pyridyl group , pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group, furanyl a heterocyclic group having 2 to 14 carbon atoms such as a group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, and the like; I can give Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formula (12), R1 and R2 are a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, a carbon atom which may have a substituent A cycloalkyl group having a number of 5 to 12 is preferred, and an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms is more preferred.

In general formula (12), the combination of R1 and R2 may be the same or different. Also, n and m are 1 or 2. When n and m are 2, they may be different groups.

In general formula (12), adjacent groups in R1 and R2 may be bonded to each other to form a ring, and the ring is either a single bond, or a nitrogen atom, an oxygen atom, or a sulfur atom. may form a ring by bonding through the atoms of Moreover, as a ring formed in that case, a 5-membered ring or a 6-membered ring is preferable.

A compound represented by the general formula (12) can be synthesized, for example, by a method such as the following reaction formula (1). In the synthesis of reaction formula (1), 5-amino-2-naphthol and cyanuric chloride are reacted in an arbitrary solvent using a basic compound such as a diisopropylethylamine compound to give intermediate 1. can get. Furthermore, intermediate 2 is obtained by reacting this intermediate 1 with an amine compound such as dibutylamine in an arbitrary solvent. Subsequently, an aromatic amine such as 2-aminobenzothiazole is diazotized by a conventional method and subjected to a coupling reaction with Intermediate 2 to obtain an azo dye represented by Exemplified Compound (B-1).

(Reaction formula 1)

In the method for synthesizing the azo dye represented by the general formula (12), if the deposited azo dye strongly adheres and interferes with stirring, an organic solvent may be mixed in order to eliminate or alleviate the problem. The organic solvent to be mixed is not particularly limited as long as it has sufficient solubility of the corresponding azo dye, and includes aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; acetone. , 2-butanone, 2-pentanone, ketones such as 3-pentanone; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran (THF), dioxane and diethyl ether; methanol, ethanol, propanol, isopropanol, butanol , pentanol, and hexanol; halogenated hydrocarbons such as dichloromethane and chloroform; N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), etc., alone or in combination can be done.

The azo dye represented by the general formula (12) is purified by column chromatography; adsorption purification by silica gel, activated carbon, activated clay, etc.; dispersion and washing with a solvent. It can be obtained by performing known purification such as recrystallization, crystallization, and salting out. Solvents used in these purification methods are not particularly limited, and alcohols such as water, methanol and ethanol; halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene and xylene; - Aliphatic hydrocarbons such as heptane can be used alone or in combination.

Specific examples of preferred compounds as the azo dyes of the present invention represented by the general formula (12) obtained by the above synthesis method are shown in the following formulas (B-1) to (B-14). , but not limited to these compounds. In the following structural formulas, some hydrogen atoms are omitted. In addition, even when stereoisomers exist, their planar structural formulas are described.

（Ｂ－１）

(B-1)

（Ｂ－２）

(B-2)

（Ｂ－３）

(B-3)

（Ｂ－４）

(B-4)

（Ｂ－５）

(B-5)

（Ｂ－６）

(B-6)

（Ｂ－７）

(B-7)

（Ｂ－８）

(B-8)

（Ｂ－９）

(B-9)

（Ｂ－１０）

(B-10)

（Ｂ－１１）

(B-11)

（Ｂ－１２）

(B-12)

（Ｂ－１３）

(B-13)

（Ｂ－１４）

(B-14)

The azo dye represented by the general formula (12) of the present invention may be used alone or in combination (for example, mixed) of two or more with different molecular structures. The weight concentration ratio of one azo dye complex having a smaller molecular structure is 0.1 to 50% by weight. One or two kinds of azo dyes are preferable.

A complex compound of an azo dye represented by the general formula (1) and a metal is obtained by reacting an azo dye represented by the general formula (12) with a positive metal ion "M" (see, for example, Patent Document 15). Positive metal ions represented by "M" include lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, cesium ion, barium ion, titanium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, aluminum ion, zirconium ion, palladium ion, silver ion, tungsten ion, gold ion, chromium ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion , aluminum ions are preferred, and nickel ions and zinc ions are particularly preferred.

In addition, the positive metal ion represented by "M" in the present invention may be used alone or in combination of two or more of the above positive metal ions. When two or more cation metal ions are combined and reacted with an azo dye, a mixture of said complex compounds is obtained.

The powder containing the azo dye-metal complex compound of the present invention may contain solvent molecules, moisture, molecular structure components other than the azo dye-metal complex compound of the present invention, and other components. be. Any of these powders may be used as they are, but those subjected to purification treatment are preferred. However, any purification method may result in the presence of a certain percentage of impurities, but any dye that can be produced in the state of the art can be used.

The colored composition containing the complex compound of the azo dye and metal represented by the general formula (1) of the present invention will be described in detail below.

As other components, in order to enhance the performance of the coloring composition of the present invention as a colorant for color filters, a surfactant, a dispersant, an antifoaming agent, a leveling agent, and other ingredients are mixed during the production of colorants for color filters. Additives, organic compounds, and the like can be added. However, the content of these additives in the coloring composition is preferably an appropriate amount, or to reduce the solubility in the solvent of the coloring composition of the present invention, or to improve more than necessary, also, color filter The content is preferably within a range that does not affect the effects of other additives of the same type used during production. These additives can be added at any time during preparation of the coloring composition.

The state of the powder of the coloring composition of the present invention and its shape can be observed using an optical microscope, a scanning electron microscope (SEM), or the like. The shape of the coloring composition of the present invention is not particularly limited, although it is usually used in a solid powder state having a shape such as crystal, microcrystal, fine powder, flake, needle crystal, granule, etc. .

By measuring the particle size distribution, surface area, pore size distribution, powder density, etc. of the powder of the coloring composition of the present invention, more detailed overall and average information on the shape of the powder can be obtained. For example, the Coulter method, which measures the electrical resistance of an electrolytic solution in which powder is dispersed, the centrifugal sedimentation method, which determines the Stokes effective diameter by measuring the absorbance of a powder dispersion, and the laser diffraction/scattering method, which analyzes the diffraction scattering pattern of a powder dispersion, etc. can be measured using The coloring composition of the present invention preferably has a particle size in the range of 0.1 μm to several mm. Although not limited, a smaller particle size is preferred for high solubility, and a median particle size distribution in the range of 0.1 to 100 μm is preferred.

By performing thermogravimetry-differential thermal analysis (TG-DTA) of the colored composition of the present invention, the decomposition onset temperature of the powder can be evaluated. As the temperature corresponding to the decomposition initiation temperature, the temperature at which the weight of the sample is reduced by a certain percentage (%) after heating may be used for evaluation. The decomposition initiation temperature is preferably 250° C. or higher, more preferably 300° C. or higher, and particularly preferably 360° C. or higher. When applied to a color filter, the decomposition initiation temperature is preferably as high as possible.

The solubility of the powder of the coloring composition in the present invention is represented by the solubility, and the solubility represents the maximum amount of the coloring composition in which the powdered coloring composition can be dissolved in a specific solvent. There is, for example, expressed in units such as "% by weight (solvent name, temperature)". Solubility can be obtained, for example, by mixing a sample in a specific solvent, stirring the solvent at a constant temperature for a certain period of time, and measuring the concentration of the prepared saturated solution. It can also be obtained by concentration measurement, such as by measurement.

The coloring composition contained in the colorant for color filters must be well dissolved or dispersed in an organic solvent containing a resin or the like in the manufacturing process of the colorant for color filters and the color filter. is preferably high. The organic solvent is not particularly limited, but specifically esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and propylene glycol monomethyl ether (PGME); propylene glycol monomethyl ether acetate (PGMEA ) and other ether esters; acetone, ketones such as cyclohexanone; methanol, ethanol and other alcohols; diacetone alcohol (DAA) and the like; benzene, toluene, xylene and other aromatic hydrocarbons; N,N-dimethylformamide (DMF), amides such as N-methylpyrrolidone (NMP); dimethylsulfoxide (DMSO) and the like. These solvents may be used alone or in combination of two or more. Among these, the colored composition containing the azo dye-metal complex compound according to the present invention preferably has excellent solubility in PGME and PGMEA, and particularly preferably has excellent solubility in PGMEA.

The solubility of the powder of the coloring composition in the present invention is measured by gradually adding the powder until it remains dissolved in a certain amount of solvent, and the concentration dissolved in propylene glycol monomethyl ether (PGME) at 25 ° C. ± 2 ° C. was obtained by measuring

The spectral characteristics (transmittance, reflectance) of the powder of the coloring composition of the present invention are important when the dye is used alone as a colorant for color filters, or when used in combination with other dyes. , which directly affects the color characteristics of the color filter. As a measurement method, there is a method of measuring the absorption (or transmission) spectrum of a solution or dispersion state, or the absorption (or transmission) spectrum of a thin film applied to a glass or transparent resin substrate. There is also a method of directly irradiating the powder with light and measuring the light reflected/scattered on the particle surface or near the particle surface.

The colorant for color filters of the present invention comprises a coloring composition containing a complex compound of an azo dye represented by the general formula (1) and a metal, and components commonly used in the production of color filters. . For general color filters, for example, in the case of a method using a photolithography process, a liquid prepared by mixing dyes such as dyes and pigments with resin components (including monomers and oligomers) and solvents is applied to glass, resin, etc. and photopolymerization using a photomask to prepare a colored pattern of a solvent-soluble/insoluble dye-resin composite film, followed by washing and heating. Also in the electrodeposition method and the printing method, a colored pattern is produced by using a mixture of a pigment and a resin or other components. Therefore, specific components in the colorant for color filters of the present invention include a complex compound of an azo dye represented by the general formula (1) and a metal, other dyes such as dyes and pigments, resin components, and organic solvents. , and other additives such as photoinitiators. In addition, these components may be selected, and other components may be added as necessary.

When the coloring composition containing the azo dye and metal complex compound of the present invention is used as a colorant for color filters, it may be used for each color filter, but is preferably used as a colorant for blue or red color filters. preferable.

The colorant for a color filter containing the coloring composition containing the azo dye-metal complex compound of the present invention may use the azo dye-metal complex compound alone. Known dyes such as other dyes or pigments may be mixed. When used as a coloring agent for a red color filter, it is not particularly limited, but C.I. I. Pigment Red 177, C.I. I. Pigment Red 209, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254 and other red pigments; other red-based lake pigments; C.I. I. Acid Red 88, C.I. I. red dyes such as Basic Violet 10, C.I. I. Pigment Yellow 139, C.I. I. A yellow pigment such as Pigment Yellow 83 may be used. When used as a colorant for a blue color filter, it is not particularly limited, but C.I. I. Basic dyes such as Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129; C.I. I. Acid dyes such as Acid Blue 9 and 74; Disperse dyes such as Disperse Blue 3, 7 and 377; Spiron dyes; Cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, and indanthrene , oxazine series, dioxazine series, xanthene series, azo series not belonging to the present invention; and other blue lake pigments.

The mixing ratio of the other dye in the colorant for color filters containing the coloring composition containing the complex compound of the azo dye and metal of the present invention is 5 to 2000% by weight with respect to the complex compound of the azo dye and metal. preferably 10 to 1000% by weight. The mixing ratio of the colorant component such as the dye in the liquid colorant for color filters is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, based on the total colorant.

As the resin component in the colorant for color filters containing the colored composition containing the complex compound of the azo dye and metal of the present invention, the color filter resin film formed by using these can be produced and used. A known material can be used as long as it has properties. Examples include acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenol (novolak) resins, other transparent resins, photocurable resins, and thermosetting resins. These monomer or oligomer components can be used in appropriate combination. Copolymers of these resins can also be used in combination. The content of the resin in these colorant for color filters is preferably 5 to 95% by weight, more preferably 10 to 50% by weight, in the case of a liquid colorant.

Other additives in the colorant for color filters containing the colored composition containing the complex compound of the azo dye and metal of the present invention include components necessary for polymerizing and curing the resin, such as photopolymerization initiators and cross-linking agents. and surfactants and dispersants necessary for stabilizing the properties of the components in the liquid colorant for color filters. Any of these can use known ones for manufacturing color filters, and are not particularly limited. The mixing ratio of the total amount of these additives in the total solid content of the colorant for color filters is preferably 5 to 60% by weight, more preferably 10 to 40% by weight.

Specific measurement methods and conditions used in the present invention are described below.

The visible absorption spectrum was measured using PGME so that the sample to be measured was a solution with a concentration of 0.02 mmol/l, and an ultraviolet-visible spectrophotometer manufactured by JASCO Corporation V-650 was used to measure the spectrum from 300 nm to 750 nm. A UV-visible spectrum was measured. The maximum absorption wavelength was read from the measurement results.

In the present invention, the 5% weight loss temperature is measured as the decomposition initiation temperature. Specifically, using a Bruker AXS TG-DTA2000SA, the temperature was measured from 25° C. to 600° C. at a rate of 10° C./min, and the temperature at which the weight of the sample decreased by 5% from the start of measurement was read.

The method for measuring the solubility (PGME, 25±2° C.) in the present invention was to measure 1 g of PGME in a 10-ml test tube under a temperature condition of 25° C.±2° C., and add 1 mg of each sample to be measured. After applying ultrasonic waves for 5 minutes, the presence or absence of undissolved samples was confirmed. This operation was repeated until undissolved samples were confirmed. Solubility was calculated when there was no undissolved sample.

EXAMPLES Hereinafter, embodiments of the present invention will be specifically described with reference to examples, but the present invention is not limited only to the following examples. The compounds obtained in the examples were identified by ¹ H-NMR analysis (nuclear magnetic resonance apparatus, JNM-ECA-600, manufactured by JEOL Ltd.).

[Synthesis Example 1] Synthesis of Azo Dye (Exemplary Compound (B-1)) Cyanuric chloride (1 g, 5.2 mmol) and 80 ml of THF were added to a 300 ml Kolben and cooled to 0° C. while stirring. Diisopropylethylamine (1.47 g, 11.3 mmol) and 5-amino-2-naphthol (0.8 g, 5.42 mmol) were added thereto. After that, the mixture was reacted at room temperature for 3 hours. After confirming the disappearance of the starting material by TLC, intermediate 1 was obtained quantitatively. 30 ml of dioxane, diisopropylethylamine (3.15 g, 24.4 mmol) and dibutylamine (1.4 g, 10.8 mmol) were added thereto. The mixture was stirred at 80° C. for 12 hours to react. After distilling off the solvent, separation was performed by column chromatography to obtain 1.6 g of Intermediate 2. (Yield 61.5%)

The diazo solution was prepared by adding sulfuric acid (6 ml), acetic acid (12 ml), water (10 ml) and thiazole (0.5 g, 3.33 mmol) to 100 ml Kolben, stirring and cooling (0° C.). Sodium nitrite (0.253 g, 3.66 mmol) was added thereto and stirred for 2 hours. Intermediate 2 (1.6 g, 3.33 mmol) was dissolved in aqueous sodium hydroxide (2.43 g, 22.9 mmol) and cooled to 0°C. The prepared diazo solution was slowly added thereto, and after stirring for 1 hour while maintaining the temperature at 0 to 5° C., the temperature was raised to room temperature and the mixture was stirred overnight. After distilling off the solvent, the solid was separated by column chromatography to obtain 0.7 g (Y.35%) of Exemplified compound (B-1).

[Synthesis Example 2] Synthesis of a complex compound of an azo dye and a metal Exemplary compound (B-1) (0.20 g, 0.3 mmol) obtained in Synthesis Example 1 was dissolved in methanol (10 ml), and nickel (II) acetate was added. A solution of tetrahydrate (0.04 g, 0.16 mmol) in water (1 ml) was added dropwise. The liquid color immediately changed to reddish purple. After stirring for 1 hour, the mixture was concentrated under reduced pressure, extracted with chloroform, and the organic layer was concentrated to obtain 0.15 g of a complex compound represented by the following formula (C-1) as a nickel complex of exemplary compound (B-1).

（Ｃ－１）

(C-1)

[Synthesis Example 3] Synthesis of a complex compound of an azo dye and a metal Exemplified compound (B-1) (0.30 g, 0.46 mmol) obtained in Synthesis Example 1 was dissolved in methanol (10 ml), and zinc (II) acetate was added. A solution of the dihydrate (0.05 g, 0.23 mmol) in water (1 ml) was added dropwise. The liquid color immediately changed to reddish purple. After stirring for 1 hour, the mixture was concentrated under reduced pressure, extracted with chloroform, and the organic layer was concentrated to obtain 0.3 g of a complex compound represented by the following formula (C-2) as a zinc complex of exemplary compound (B-1).

（Ｃ－２）

(C-2)

[Examples 1 and 2]
For the complex compounds (C-1) and (C-2) obtained in Synthesis Example 2 and Synthesis Example 3, the maximum absorption wavelength in the visible absorption spectrum, the 5% weight loss temperature (decomposition start temperature) and solubility (wt%, PGME, 25±2° C.) were measured. Those results are shown in Table 1.

[Comparative Example 1]
For comparison, the exemplary compound (B-1) obtained in Synthesis Example 1 was measured in the same manner as in Example 1 for the maximum absorption wavelength of the visible absorption spectrum, 5% weight loss temperature (decomposition initiation temperature) and solubility (weight %, PGME, 25±2° C.) were measured. Table 1 shows the measurement results.

[Comparative Example 2]
For comparison, for AcidRed88 represented by the following formula (D-1), in the same manner as in Example 1, the maximum absorption wavelength of the visible absorption spectrum, 5% weight loss temperature (decomposition initiation temperature) and solubility (% by weight, PGME, 25±2° C.) was measured. Table 1 shows the measurement results.

（Ｄ－１）

(D-1)

As shown in Table 1, the azo dye-metal complex compound of the present invention example has a higher solubility in PGME (5% by weight) than the existing dye (Comparative Example 2). . Furthermore, compared with the compound before complexation (Comparative Example 1), the heat resistance (5% weight loss temperature) is improved while almost maintaining the solubility in PGME. Also, the maximum absorption wavelength is around 560 nm, which is suitable as a red or blue color filter dye. Therefore, the complex compound of the azo dye and metal of the present invention has high solubility in PGME organic solvents and excellent heat resistance. Since it has a solid (powder, etc.) state necessary for exhibiting good solubility or dispersibility, it is suitable as a colorant for use in color filters. Therefore, the color filter obtained using the coloring agent is excellent in color development (color gamut, brightness, contrast ratio, etc.).

The complex compound of an azo dye and a metal according to the present invention is useful as a colorant for color filters, and is suitable as a coloring agent for use in color filters as a coloring composition. A color filter having excellent color development properties (color gamut, brightness, contrast ratio, etc.) can be obtained using the colorant.

Claims (5)

A complex compound of an azo dye and a metal represented by the following general formula (1) ,
A complex compound represented by the general formula (1), wherein the azo dye is an azo dye represented by the following general formulas (9) to (11).

[Wherein, Ar1 and Ar2 are each independently
represents an optionally substituted aromatic hydrocarbon group or heteroaromatic ring group having 3 to 20 atoms consisting of one or a plurality of carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms;
R1 to R2 are each independently a hydrogen atom,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, or
It represents an optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms, and R1 and R2 may be combined to form a ring.
n and m are 1 or 2;
When n and m are 2, they may be different groups.
X1, X2, and X3 each independently represent an amino group, an ether group, a sulfonyl group, a sulfoxide group, an ester group, an amide group, a urea group, a thioether group, a thioester group, a thioamide group, a thiourea group, a urethane group, and a sulfonate ester. group, sulfonamide group and carbamoyl group.
M represents a positive metal ion. q represents an integer of 1 to 4; ]

[In the formula, R1, R2, n and m, X1, X2, and X3 shall be described in the general formula (1).
R10 to R13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, —SO ₃ ⁻ ,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted cycloalkyl group having 3 to 20 carbon atoms,
an optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms,
an optionally substituted cycloalkoxy group having 3 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms,
an optionally substituted acyl group having 1 to 20 carbon atoms,
an optionally substituted amino group having 0 to 20 carbon atoms,
an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or
It represents an optionally substituted heterocyclic group having 2 to 20 carbon atoms.
a is an integer of 1 to 4, b to d are integers of 1 to 6,
When a to d are 2 or more, each may be a different group. ] 2. The complex compound according to claim 1 , wherein the solubility in propylene glycol monomethyl ether (PGME) at 25° C.±2° C. is 5% by weight or more when the powder is added to the solvent and the solubility is measured. A coloring composition containing the complex compound according to claim 1 or 2 . A colorant for color filters, comprising the coloring composition according to claim 3 . A color filter using the colorant for color filters according to claim 4 .