TWI700335B - Coloring agent compound, coloring composition including the same, color filter including the coloring composition, and display device including the same - Google Patents

Abstract

Provided are a coloring agent and a coloring composition including the same. More particularly, provided are a coloring agent of a novel structure, which shows excellent color properties and heat resistance, and a coloring composition including the same, thereby being applicable to manufacturing of a color filter and a display device including the same.

Description

Colorant compound, coloring composition including the compound, And a color filter including the coloring composition and a display device including the color filter [Cross reference of related applications]

This application claims the Korean patent application No. 10-2017-0100549 filed with the Korean Intellectual Property Office on August 8, 2017, and the Korean patent application filed with the Korean Intellectual Property Office on June 20, 2018 The right of No. 10-2018-0071074, the disclosure content of the Korean patent application is incorporated into this case for reference.

The present invention relates to a coloring agent compound and a coloring composition including the compound. More specifically, the present invention relates to a coloring agent compound with a novel structure having excellent color properties and heat resistance and a coloring composition including the compound.

Color filters include displaying red (R) color, green (G) color and blue (B) The corresponding unit pixel of the color, the unit pixel is formed on a transparent substrate such as glass, and used in, for example, liquid crystal display devices (LCD), organic light emitting diodes (organic light emitting diodes), etc. Color images are achieved in display devices such as diode, OLED).

The coloring of the corresponding unit pixel applied to such color filters is composed of fine particles in the form of pigments or dyes. In many cases, red, green, and blue colors are produced by the following methods: appropriately mixing coloring materials such as coloring or coloring agents that show different colors, instead of using red Corresponding single colorants of color, green color and blue color.

Recently, in the field of liquid crystal displays, the demand for large screens and high resolution has rapidly increased, and therefore, research has been concentrated on achieving high-performance color filters that meet the above-mentioned needs.

However, the known pigment-type coloring materials exhibit poor solubility and dispersibility in the composition due to their structural limitations. In addition, particles that have been dissolved in the composition can re-aggregate to form coarse particles and other foreign matter.

Therefore, it is difficult for the color filter produced from the well-known pigment-based coloring material to exhibit characteristics such as color purity, color reproducibility, brightness, and contrast at a level that meets the requirements for large screens and high definition.

At the same time, color filters basically require heat resistance, light resistance, and so on. However, the known pigment-based coloring materials also have limitations in improving heat resistance and light resistance due to their structural limitations.

In order to overcome the above limitations, the present invention provides examples of colorant compounds and coloring compositions comprising the compounds, the colorant compounds having structures that are not generally known.

The embodiment of the present invention provides a coloring agent compound represented by the following formula 1:

In Formula 1, A is represented by the following Formula 2a or Formula 2B, R ¹ to R is at least one ⁶ represented by the following formula 3, in R ¹ to R ^6, are not represented by the following formula other R 3 represents ¹ to R ^{6 is} each independently hydrogen; substituted or unsubstituted C1 to C20 alkyl; substituted or unsubstituted C1 to C20 alkoxy; substituted or unsubstituted C1 to C20 hydroxyalkyl; Substituted or unsubstituted C6 to C30 aryl; substituted or unsubstituted C7 to C30 arylalkyl; substituted or unsubstituted C7 to C30 alkylaryl; or substituted or unsubstituted C2 to C30 heteroaryl;

In formula 2a and formula 2b, X ¹ are the same or different from each other and are hydrogen; halogen atom; substituted or unsubstituted C1 to C20 alkyl group; substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C1 to C20 hydroxyalkyl; substituted or unsubstituted C6 to C30 aryl; substituted or unsubstituted C7 to C30 arylalkyl; substituted or unsubstituted C7 to C30 alkylaryl; or substituted or unsubstituted C2 to C30 heteroaryl; [Formula 3]*-Q ¹ -Q ² -R ⁷ -B

In formula 3, Q ¹ is O or NH; Q ² is a direct bond or CO; R ⁷ is a direct bond or a C1 to C12 alkylene group; B is a C6 to C30 aryl group substituted with one or more hydroxyl groups; or A C7 to C30 alkyl aryl group substituted with one or more hydroxyl groups.

In addition, another embodiment of the present invention provides a coloring composition including the colorant compound, a binder resin, a polymerizable compound, and a photoinitiator.

Since the coloring agent compound provided in the embodiments of the present invention is different from the known compounds, it has a structure including a specific moiety, so the coloring agent compound can meet the requirements of large screens and high definition It exhibits characteristics such as color purity, color reproducibility, brightness, and contrast at the required level, and can also exhibit excellent basic performance such as heat resistance and light resistance.

The coloring composition provided in another embodiment of the present invention includes the above-mentioned colorant compound, and when the coloring composition is used to manufacture a color filter, it can be manufactured in terms of color characteristics such as color reproducibility, heat resistance, High-resolution, large-area color filter with excellent light resistance. Another embodiment of the present invention provides a display device including the color filter.

The present invention is implemented as a coloring agent compound and a coloring composition including the compound. With reference to the following detailed examples, the advantages and features of the embodiments and the methods for achieving them will become apparent. However, the present invention is not limited to the examples disclosed below, but can be implemented in various forms. These examples are provided to fully explain the present invention and fully convey the scope of the present invention to those skilled in the present invention. This application is intended to be limited only by the terms of the patent scope of the present invention, and should not be construed as limiting the scope of the present invention.

Hereinafter, before the detailed description of the embodiments of the present invention, the expressions and terms commonly used herein are defined.

First of all, * as used herein means a bond to another substituent.

The term "substituted or unsubstituted" as used herein means substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; halogen; nitrile; nitro; hydroxy ；Carbonyl; Ester; Amino; Amino; Phosphine oxide; Alkoxy; Aryloxy; Alkylthiooxy; Arylthiooxy; Alkylsulfonate; Arylsulfonate Group; Silyl; Boron; Alkyl; Cycloalkyl; Alkenyl; Aryl; Aralkyl; Aralkenyl; Alkylaryl; Alkylamino; Aralkylamino; Heteroarylamino ; Arylamino; arylphosphino; and heterocyclic groups containing one or more of N atoms, O atoms and S atoms, or means substituted or unsubstituted by connecting the substituents shown above Substituent substitution obtained by two or more substituents. For example, the "substituent obtained by linking two or more substituents" may be biphenyl. In other words, Biphenyl can be interpreted as an aryl group or a substituent obtained by connecting two phenyl groups.

基(chrycenyl group)、茀基(fluorenyl group)等，但並非僅限於此。 In the present disclosure, the "aryl group" may be a monocyclic aryl group or a polycyclic aryl group having 6 to 30 carbon atoms, 6 to 20 carbon atoms, or 6 to 12 carbon atoms. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but it is not limited thereto. Polycyclic aryl groups can be naphthyl (naphthyl group), anthracenyl group (anthracenyl group), phenanthryl group (phenanthryl group), pyrenyl group (pyrenyl group), perylenyl group (perylenyl group),

Chrycenyl group, fluorenyl group, etc., but not limited to this.

In the present disclosure, the alkyl group may be a linear or branched alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms. Specific examples of alkyl groups may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, second butyl, 1-methyl- Butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tertiary octyl Base, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl Group-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but not limited to these.

In the present disclosure, the aryl group in the arylalkyl group and the alkylaryl group is the same as the above-mentioned aryl group. In the present disclosure, the alkyl group in the arylalkyl group and the alkylaryl group is the same as the above-mentioned alkyl group.

Below, based on the expressions and terms defined above, the present invention will be explained in detail. Ming's embodiment.

Colorant compound

The structure and advantages of colorant compounds

The colorant compound according to the embodiment of the present invention may have a novel structure, wherein the compound is based on 1) quinophthalone or a derivative compound thereof, and 2) a specific substituent is introduced into the basic skeleton.

Specifically, the coloring agent compound according to the embodiment of the present invention is represented by the following formula 1:

1) In Formula 1, A is represented by the following Formula 2a or Formula 2b, which indicates that the colorant compound according to the embodiment of the present invention is based on quinophthalone or its derivative compound, thereby expressing yellow color:

In formula 2a and formula 2b, X ¹ are the same or different from each other and are hydrogen; halogen atom; substituted or unsubstituted C1 to C20 alkyl group; substituted or unsubstituted C1 to C20 alkoxy group; Substituted or unsubstituted C1 to C20 hydroxyalkyl; substituted or unsubstituted C6 to C30 aryl; substituted or unsubstituted C7 to C30 arylalkyl; substituted or unsubstituted C7 to C30 alkylaryl; or substituted or unsubstituted C2 to C30 heteroaryl.

Hereinafter, for convenience, "quinophthalone or its derivative compound" is referred to as "quinophthalone-based compound".

2) At the same time, in Formula 1, at least one of R ¹ to R ⁶ is represented by the following Formula 3, and among R ¹ to R ⁶ , other R ¹ to R ^{6 that} are not represented by the following Formula 3 are respectively Independently hydrogen; substituted or unsubstituted C1 to C20 alkyl; substituted or unsubstituted C1 to C20 alkoxy; substituted or unsubstituted C1 to C20 hydroxyalkyl; substituted or unsubstituted Substituted C6 to C30 aryl; substituted or unsubstituted C7 to C30 arylalkyl; substituted or unsubstituted C7 to C30 alkylaryl; or substituted or unsubstituted C2 to C30 Heteroaryl, which indicates that the coloring agent compound according to the embodiment of the present invention is a compound in which a substituent represented by the following formula 3 is introduced into at least one position of a quinophthalone-based compound: [Formula 3]*─Q ¹ ─Q ² ─R ⁷ ─B

In formula 3, Q ¹ is O or NH; Q ² is a direct bond or CO; R ⁷ is a direct bond or a C1 to C12 alkylene group; B is a C6 to C30 aryl group substituted with one or more hydroxyl groups; or A C7 to C30 alkyl aryl group substituted with one or more hydroxyl groups.

In this regard, the coloring agent compounds according to the embodiments of the present invention incorporate i) a hydrophilic Q ¹ part, a Q ² part (in the case of CO) and B and ii) a substituent having a high molecular weight at the same time (Formula 3 ), therefore, the colorant compound may have improved characteristics, such as solubility, heat resistance, etc., compared to the compound without introducing the above-mentioned substituents.

i) Specifically, during the preparation of the composition for the color filter, for example, a dispersing agent is generally added to improve the dispersibility of the colorant compound in the composition.

However, in the coloring agent compound according to the embodiment of the present invention, a substituent including a hydrophilic Q ¹ part, a Q ² part (in the case of CO), and B (Formula 3) is introduced, and therefore, compared to not For the compound introduced with the above-mentioned substituent, the dispersibility of the colorant compound in the composition can be improved. When a hydrophilic solvent is included in the composition, this effect can be achieved more excellently.

Therefore, unlike the general situation, when preparing a composition including the colorant compound according to the embodiment of the present invention, a smaller amount of additives such as a dispersant or no additives may be used, and re-aggregation between the colorant compounds may be suppressed Or other foreign objects.

In addition, a color filter based on the above composition can exhibit excellent characteristics such as color purity, brightness, and contrast by appropriately combining the absorption spectrum and transmission spectrum of the color filter with the spectrum of the light source.

ii) At the same time, in the coloring agent compound according to the embodiment of the present invention, a substituent containing a C6 to C30 aryl group or a C7 to C30 alkyl aryl group (Formula 3) is introduced, and therefore, compared to not introducing For compounds with such substituents, the molecular weight of the colorant compound can be increased.

Therefore, the colorant compound according to the embodiment of the present invention can be prepared as a composition with improved heat resistance based on the increased molecular weight of the colorant composition.

In addition, the color filter based on the composition can exhibit stable display performance, because the color purity, brightness, contrast, etc. do not change rapidly during the heat treatment process of the embodiment.

In short, the coloring agent compound according to the embodiment of the present invention can i) exhibit a yellow color, because the compound is based on a quinophthalone-based compound, and can ii) have improved solubility, which is because The compound is introduced with a substituent represented by the following formula 3, and thus exhibits excellent characteristics such as color purity, color reproducibility, contrast, heat resistance, etc., compared to a compound without the introduction of the above substituent.

With reference to the examples detailed below, these advantages and features and the methods for achieving them will become apparent.

Examples of colorant compounds

Hereinafter, the coloring agent compound according to the embodiment of the present invention will be briefly explained based on the example explained in detail below. However, the following description is only for illustrative purposes, and the scope of the present invention is defined by the scope of patent application, as explained above.

Compounds contained in general pigments do not have bulky substituents, and therefore most general pigments are insoluble in solvents. Therefore, a general pigment is dispersed in a particle state without being dissolved in a solvent, and therefore, the pigment absorption includes a new absorption spectrum generated by the attraction force between the compound molecules and a broad spectral region of the inherent absorption spectrum of the compound molecules.

To solve this problem, in the embodiment of the present invention, a bulky substituent is introduced into the colorant compound of Formula 1.

Specifically, according to an embodiment of the present invention, in Formula 2a and Formula 2b, X ¹ may be the same as each other and be hydrogen. In addition, according to an embodiment of the present invention, B of formula 3 can be represented by the following formula 4:

In Formula ^{4, R a, R b, R} c, R d and R ^e in any one or more of a hydroxyl group (-OH), and the others are each independently hydrogen, C1 to C20 linear alkyl group or C3 to C20 branched alkyl.

When the bulky substituent of Formula 4 is introduced into the colorant compound of Formula 1, the solubility of the compound in the solvent can be improved compared to the compound without the bulky substituent.

Here, the increase in solubility can help to improve color purity, color reproducibility, brightness, contrast, etc. by reducing the attraction between molecules of the coloring agent compound of Formula 1 to generate a new absorption spectrum.

In addition, the improved solubility can help to inject other materials required to improve the handleability of the color pattern by significantly reducing the amount of materials (eg, dispersants, etc.) required for dispersion of the colorant compound of Formula 1.

Specifically, when the bulky substituent of Formula 4 has a hindered structure in which a hydroxyl group is placed between two different branched alkyl groups, radicals involved in molecular degradation ) And singlet oxygen can react with the hindered structure, thus improving the stability of the chromophore compared to compounds without introducing hindered structure.

Specifically, according to an embodiment of the present invention, in Formula 4, R ^c may be a hydroxyl group; R ^a and R ^e each independently may be hydrogen. R ^b and R ^d may each independently be a C3 to C20 branched alkyl group, specifically a C3 to C10 branched alkyl group, and more specifically a C3 to C6 branched alkyl group.

More specifically, R ^b and ^{Rd of} Formula 4 may each independently be a C4-branched alkyl group, and in this case, Formula 4 may be placed at the position of R ⁶ of Formula 1, and Formula 1 R ¹ to R ⁵ may each independently be hydrogen.

As an example of the above situation, the compound represented by Formula 1 may be any one selected from the group consisting of the following compounds, but is not limited to this:

Various methods known in the art (including the following preparation Example) To prepare the coloring agent compound of Formula 1. Therefore, the method for preparing the colorant compound of Formula 1 is not particularly limited.

Coloring composition

According to another embodiment of the present invention, a coloring composition including the coloring agent compound of Formula 1 is provided.

Here, the detailed description and specific examples of the coloring agent compound of Formula 1 are the same as those described above. Hereinafter, the composition including the coloring agent compound of Formula 1 will be described in detail, but any description overlapping with the above description will be omitted.

Based on 100% by weight of the solid contents contained in the coloring composition, it may contain about 10% by weight or more than 10% by weight or about 15% by weight or more than 15% by weight or about 20% by weight or more than 20% by weight % And about 50% by weight or less than 50% by weight or about 40% by weight or about 30% by weight or less than 30% by weight of the coloring agent compound. If the content of the colorant compound is too low, the color purity may be reduced, and if the content is too high, the curing reaction of the resin composition may not proceed correctly. From this point of view, it is preferable to include a coloring agent compound in the above-mentioned range.

When preparing the coloring composition according to the embodiment of the present invention, the coloring agent compound of Formula 1 may be used alone or in a combination of two or more.

In addition, the coloring composition of the present invention, in addition to the coloring agent compound of Formula 1, may further include any other known coloring agent compounds as necessary.

For example, in addition to the coloring agent compound of Formula 1, the coloring composition of the present invention may also include at least one of a dye and a pigment. With In general, the dye and the pigment may include one or more compounds showing any one of yellow, red and green colors.

More specifically, the compound exhibiting a yellow color may include a compound selected from the group consisting of metal-complex compounds, azo compounds, quinophthalone compounds, isoindoline ( One or more compounds in the group consisting of isoindoline compounds and styryl compounds.

The compound showing a red color may include selected from metal-complex (metal-complex) based compounds, azo (azo) based compounds, xanthene based compounds, diketopyrrolopyrrole based compounds, One or more compounds in the group consisting of anthraquinone compounds and perylene compounds.

The compound exhibiting a green color may include one or more compounds selected from the group consisting of metal-complex compounds, triarylmethane compounds, and anthraquinone compounds.

The pigment may include one or more selected from the group consisting of: the yellow pigment group, including PY129, PY138, PY139, PY150, and PY185; the red pigment group, including PR48, PR 48:1, PR 48 : 2, PR 48: 3, PR 48: 4, PR 177, PR 179, PR 207, PR 254, PR 255, PR 264 and PR 269; and the green pigment group, including PG 7, PG 36, PG 58 and PG 59.

In addition, the coloring composition according to the embodiment of the present invention may further include a binder resin, a polymerizable compound, and a photoinitiator.

The polymer resin is not particularly limited and polymer resins commonly used in the technology of the present invention can be used. For example, alkali-soluble resins can be used.

Specific examples of alkali-soluble resins may include (meth)acrylic resins, acrylamide resins, novolac resins, etc., and for example, a weight average molecular weight (Mw) of 3,000 g/mol to 150,000 g/mol may be used (g/mol) resin, but the present invention is not limited to this.

Based on 100% by weight of the solid content contained in the coloring composition, about 3% by weight or more than 3% by weight or about 5% by weight or more than 5% by weight or about 10% by weight or more than 10% by weight and about 30% by weight may be included. % By weight or less than 30% by weight or about 20% by weight or about 15% by weight or less than 15% by weight of the polymer resin, but the present invention is not limited to this.

The polymerizable compound is not particularly limited, and polymerizable compounds commonly used in the art to which the present invention belongs can be used. For example, a photopolymerizable compound having an ethylenic unsaturated group can be used. The compound having an ethylenically unsaturated group may be an acrylate-based compound.

More specific examples thereof may include one or more compounds selected from the group consisting of: pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, ethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate, but the present invention is not limited to these.

Based on 100% by weight of the solid content contained in the coloring composition, it may contain about 30% by weight or more than 30% by weight or about 40% by weight or more than 40% by weight % Or about 50% by weight or more than 50% by weight and about 80% by weight or less than 80% by weight or about 70% by weight or about 60% by weight or less than 60% by weight of the polymerizable compound, but the present invention is not limited to this .

The photoinitiator, ie, the photopolymerization initiator, is not particularly limited, and the photoinitiator commonly used in the technology of the present invention can be used. For example, the photoinitiator may include one or more compounds selected from the group consisting of: 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine, 2 ,4-Trichloromethyl-(4'-methoxystyryl)-6-triazine, 2,4-trichloromethyl-(fipney)6-triazine, 1-hydroxycyclohexylbenzene Ketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy)propyl ketone, benzophenone and 2,4,6-trimethylaminobenzophenone, etc., but not only Limited to this.

The photoinitiator may be included in an amount of about 0.1% by weight to about 10% by weight based on 100% by weight of the solid content contained in the coloring composition, but the present invention is not limited to this.

The coloring composition of the present invention may further include a solvent to improve coating properties and processability.

For example, the solvent may include one or more compounds selected from the group consisting of methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol two Ethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3 -Methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, Ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate and dipropylene Glycol monomethyl ether, but not limited to this.

The content of the solvent can be controlled by taking into account the coating properties and processability, and therefore the content of the solvent is not particularly limited, but based on 100 parts by weight of the solid content contained in the coloring composition, it may contain from about 50 parts by weight to about 500 parts by weight of solvent.

At the same time, the coloring composition may further include additives that may be included in known coloring compositions for color filters, such as curing accelerators, thermal polymerization inhibitors, dispersants, antioxidants, ultraviolet absorbers, Leveling agents, photosensitizers, plasticizers, adhesion promoters, fillers, surfactants, etc.

Examples of curing accelerators may include one or more selected from the group consisting of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto- 1,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol tetra (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetra ( 2-mercaptoacetate), pentaerythritol tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), three Hydroxymethylethane tris(2-mercaptoacetate) and trimethylolethane tris(3-mercaptopropionate), but not limited to them, and curing accelerators can include those commonly known in the art Known curing accelerator.

Color filter

The colorant compound represented by Formula 1 can be used to manufacture a color filter by a method known in the art of the present invention (for example, by printing or photolithography).

In this regard, yet another embodiment of the present invention provides a color filter containing a colorant compound.

For example, according to the photolithography method, a transparent substrate is coated with a colored composition by spray coating, spin coating, slit coating, roll coating, immersion, or the like. The coated substrate is selectively subjected to an exposure process through a mask having a predetermined pattern. At the same time, a prebake process and/or a post bake process can be further performed. After exposure, the coloring composition is developed to form a desired photoresist pattern. After washing and drying the developed substrate, a color filter with a desired photoresist pattern can be obtained.

As described above, the color filter manufactured using the colorant composition can exhibit excellent characteristics such as color purity, color reproducibility, contrast, heat resistance, etc., because the colorant composition (formula 1) is based on 1) A quinophthalone-based compound that exhibits a yellow color, and 2) Compared with a compound that does not introduce a bulky substituent (Formula 3), by introducing a bulky substituent into it (Formula 3) and has improved solubility.

Specifically, when the bulky substituent has a hindered structure in which a hydroxyl group is placed between two different branched alkyl groups, radicals and singlet states are involved when the molecule is degraded. ) Oxygen can react with the hindered structure, and can improve the stability of the chromophore compared to the compound without introducing the hindered structure.

Therefore, when the coloring composition of the present invention is used, a color filter with high reliability and high resolution can be manufactured.

Hereinafter, the actions and effects of the present invention will be described in more detail with reference to specific examples of the present invention. However, these examples are for illustrative purposes only, and the scope of the present invention It is not intended to be limited by these examples.

<Example of synthetic colorant compound> Preparation Example 1. Synthesis of Intermediate A

30 grams (g) (188.45 millimoles (mmol)) intermediate 1, 27.93 grams (188.45 millimoles) intermediate 1-A, 60 grams of benzoic acid (bvenzoic acid) and 200 grams of methyl benzoate (methyl The benzoate was put into a 500-ml one-neck round bottom flask (1-neck RBF) and stirred at 180°C for 10 hours. Then, this solution was cooled to room temperature, and 2000 ml of MeOH was added thereto, followed by stirring. The precipitate generated during this process was filtered under reduced pressure, washed with MeOH, and dried in a vacuum oven at 80° C. for 24 hours to obtain Intermediate A. In this regard, it was confirmed by mass spectrum (MS) analysis that the molecular weight of the obtained intermediate A was 289 grams/mole (g/mol).

Preparation Example 2. Synthesis of Compound 1

Put 30 ml nitrobenzene and 3.89 g (15.56 millimoles) of intermediate 1-B into a 100 ml two-neck round bottom flask (2-neck RBF), and then proceed Stir. Then, 5.55 g (46.67 millimoles) of SOCl ₂ was slowly added dropwise and allowed to react at 95°C for 2 hours. Then, nitrogen was injected for 30 minutes to remove residual SOCl ₂ and HCl. Then, the solution was cooled to room temperature, and then 3 g (10.37 mmol) of Intermediate A and 3.15 g (31.11 mmol) of triethylamine were added and reacted at 90°C. hour. Next, this solution was added to diethyl ether (diethyl ether), and then stirred. The precipitate generated during the process was filtered under reduced pressure, washed with diethyl ether, and separated and purified by column chromatography to obtain compound 1. In this regard, it was confirmed by mass spectrometry that the molecular weight of Compound 1 was 521 grams/mole (g/mol).

Preparation Example 3. Synthesis of Compound 2

Compound 2 was prepared in the same manner as Preparation Example 2 except that Intermediate 1-C was used instead of Intermediate 1-B.

Preparation Example 4. Synthesis of Intermediate B

The intermediate B was prepared in the same manner as in Preparation Example 1, except that the intermediate 1-D was used instead of the intermediate 1-A.

Preparation Example 5. Synthesis of Compound 3

Compound 3 was prepared in the same manner as in Preparation Example 2 except that Intermediate B was used instead of Intermediate A.

Preparation Example 6. Synthesis of Compound 4

Compound 4 was prepared in the same manner as in Preparation Example 3 except that Intermediate B was used instead of Intermediate A.

Preparation Example 7. Synthesis of Intermediate C

The intermediate C was prepared in the same manner as in Preparation Example 1, except that the intermediate 1-E was used instead of the intermediate 1-A.

Preparation Example 8. Synthesis of compound 4

Compound 5 was prepared in the same manner as in Preparation Example 2, except that Intermediate C was used instead of Intermediate A.

Preparation Example 9. Synthesis of Compound 5

Compound 6 was prepared in the same manner as Preparation Example 3 except that Intermediate C was used instead of Intermediate A.

Preparation Example 10. Synthesis of Intermediate D

Put 250 ml of methylene chloride and 30 g (189.63 millimoles) of Intermediate 2 into a 500 ml two-neck round bottom flask (2-neck RBF), and then stir. Then, 57.567 g (568.90 millimoles) of triethylamine was slowly added dropwise and stirred at room temperature for 30 minutes. Next, 50.97 g (189.63 millimoles) of Intermediate 1-F was slowly dropped, and reacted at 45°C for 3 hours. 500 ml of deionization water (DI-water) was added thereto, and the organic layer formed by phase separation was dried via MgSO ₄ . The solvent was removed under reduced pressure, and the intermediate D was obtained by separation and purification by column chromatography. In this regard, it was confirmed by mass spectrometry that the molecular weight of the obtained intermediate D was 390 grams/mole (g/mol).

Preparation Example 11. Synthesis of Intermediate E

Intermediate E was prepared in the same manner as in Preparation Example 10 except that Intermediate 1-G was used instead of Intermediate 1-F.

Preparation Example 12. Synthesis of Compound 7

Add 3 grams (7.66 millimoles) of Intermediate D and 1.15 grams (7.74 millimoles) of Intermediate 1-A to 5 grams of benzoic acid in a 100 ml one-neck round bottom flask (1-neck RBF) ) And 20 ml of methyl benzoate, and then stirred. The solution was reacted at 180°C for 10 hours and cooled to room temperature. Then, this solution was added to 200 ml of MeOH, and then stirred. The precipitate generated during this process was filtered under reduced pressure, and separated and purified by column chromatography to obtain compound 7. In this regard, it was confirmed by mass spectrometry that the molecular weight of the obtained compound 7 was 520 grams/mole (g/mol).

Preparation Example 13. Synthesis of Compound 8

Compound 8 was prepared in the same manner as in Preparation Example 12 except that the following Intermediate E was used instead of Intermediate D.

Preparation Example 14. Synthesis of Compound 9

Compound 9 was prepared in the same manner as Preparation Example 12 except that the following Intermediate 1-D was used instead of Intermediate 1-A.

Preparation Example 15. Synthesis of Compound 10

Compound 10 was prepared in the same manner as in Preparation Example 13, except that the following Intermediate 1-D was used instead of Intermediate 1-A.

Preparation Example 16. Synthesis of Compound 11

Compound 11 was prepared in the same manner as Preparation Example 12 except that Intermediate 1-E was used instead of Intermediate 1-A.

Preparation Example 17. Synthesis of Compound 12

Compound 12 was prepared in the same manner as Preparation Example 13, except that Intermediate 1-D was used instead of Intermediate 1-A.

Preparation Example 18. Synthesis of Intermediate F

Intermediate F was prepared in the same manner as in Preparation Example 10 except that Intermediate 1 and Intermediate 1-H were used instead of Intermediate 2 and Intermediate 1-F. In this regard, it was confirmed by mass spectrometry that the molecular weight of the obtained intermediate F was 377 grams/mole (g/mol).

Preparation Example 19. Synthesis of Compound 13

Compound 13 was prepared in the same manner as in Preparation Example 12 except that Intermediate F was used instead of Intermediate D. In this regard, it was confirmed by mass spectrometry that the molecular weight of the obtained compound 13 was 507 grams/mole (g/mol).

Preparation Example 20. Synthesis of Compound 14

Compound 14 was prepared in the same manner as in Preparation Example 12 except that Intermediate F and Intermediate 1-D were used instead of Intermediate D and Intermediate 1-A, respectively. In this regard, it was confirmed by mass spectrometry that the molecular weight of the obtained compound 14 was 557 grams/mole (g/mol).

Comparative Example Compound 1

PY 138 (BASF, Paliotol® Yellow L (Yellow L) 0960 HD) was used as the comparative example compound 1.

<Example of preparing coloring composition> Comparative example 1

The following components were mixed to prepare a total of 100 grams of coloring composition: 5.554 grams of coloring agent compound 1 and 10.376 grams of a copolymer of benzyl methacrylate and methacrylic acid as a binder resin (molar ratio of 70: 30. The acid value is 113KOH mg/g, the weight average molecular weight measured by gel permeation chromatography (GPC) is 20,000 grams/mole (g/mol), and the molecular weight distribution (polymer dispersion index) (polymer dispersion index, PDI) is 2.0, solid content (solid content, SC) is 25%, contains solvent propylene glycol monomethyl ether acetate (Propylene Glycol Monomethyl Ether Acetate, PGMEA), 12.443 grams as polymerizable compound Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku), 2.018 grams of I-369 (BASF) as a photoinitiator, 1.013 grams of F-475 ( DIC (DIC)) and 68.593 grams of solvent propylene glycol monomethyl ether acetate (PGMEA).

Comparative Example 2, Examples 1~4, Comparative Examples 3~4, Examples 5~8, Comparative Example 5, Example 9

Each coloring composition was prepared in the same manner as in Example 1, except that 5.554 g of each of colorant compound 2 to colorant compound 14 was used instead of 5.554 g of colorant compound 1.

Comparative example 6

A coloring composition was prepared in the same manner as in Example 1, except that 5.554 g of Comparative Example Compound 1 was used instead of 5.554 g of Coloring Agent Compound 1.

<Experimental example> Evaluation of heat resistance and light transmittance

The coloring compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were evaluated for heat resistance and light transmittance.

In detail, the coloring compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were spin-coated onto a glass substrate (5 cm×5 cm (cm)) and pre-baked at 100°C Bake (pre bake, prB) for 100 seconds to form a film. The gap between the photomask and the substrate on which the film is formed is 300 microns (μm), and exposure is performed on the entire surface of the substrate at an exposure dose of 40 millijoules/cm² (mJ/cm ² ).了Illumination.

The exposed substrate was developed in a developing solution (KOH, 0.05%) for 60 seconds and post bake (PB) at 230° C. for 20 minutes to obtain a substrate with a color pattern formed.

In order to evaluate the light transmittance and heat resistance, a spectrophotometer (MCPD, Otsuka Co., Ltd.) was used to obtain the pre-baked in the visible light range of 380 nanometers (nm) to 780 nanometers ( pre bake, prB) Absorption spectrum of the substrate. In addition, the same equipment was used to obtain the transmission spectrum of the post bake (PB) substrate in the same measurement range.

Using the absorption spectra obtained during the pre-baking and post-baking treatments and the E (L*, a*, b*) obtained by the C light source backlight, △Eab was calculated according to the following equation 1, and the results are shown in Table 1. . For reference, in Table 1, when the ΔE value is smaller, the composition has more excellent color heat resistance (evaluation of heat resistance), and can A composition with ΔE<3 was used as a color (evaluation of light transmittance) for the color filter.

[Equation 1]△Eab(L*,a*,b*)={(△L*) ² +(△a*) ² +(△b*) ² } ^1/2

In Table 1, it was confirmed that the colorant compound of Comparative Example 6 was a commercially available material having a small color change (ΔEab) of 0.31.

It was also confirmed that the colorant compounds of Examples 1 to 9 also have a color change (△Eab) of less than 3 and have excellent heat resistance, reaching a level similar to that of the colorant compound of Comparative Example 1, and therefore The colorant compound can be used as a colorant for a color filter.

Evaluation of solubility

The coloring compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were evaluated for solubility.

In detail, each colorant compound was dissolved in Propylene glycol monomethyl ether acetate (PGMEA) at 25°C, and its solubility was evaluated. The results are shown in Table 2.

In Table 2, solubility of 3% or more is marked as ○, solubility of less than 3% and 1% or more than 1% is marked as △, and solubility of less than 1% is marked as X.

In Table 2, it is confirmed that the solubility of the coloring agent compound of Comparative Example 6 is less than 1%, while the solubility of the coloring agent compound of Examples 1 to 9 is at least 1%, and can reach a solubility of 3% or more.

These results in combination with the above description indicate that each colorant compound of Examples 1 to 9 shows high solubility, because the colorant compound is different from Comparative Example 1 in that it has a bulky substituent. The substituent has a hydroxyl group Hindered structure placed between two different branched alkyl groups.

The high solubility of the colorant compounds of Examples 1 to 9 reduces the new absorption spectrum due to the attraction between the molecules of the colorant compound, thus helping to achieve excellent color purity, color reproducibility, brightness, and contrast Wait.

In addition, since each of the colorant compounds of Examples 1 to 9 has a hindered structure in which a hydroxyl group is placed between two different branched alkyl groups, radicals and radicals involved in molecular degradation The singlet oxygen can react with the hindered structure, and can improve the stability of the chromophore compared to the compound without introducing the hindered structure.

Claims (17)

A coloring agent compound represented by the following formula 1:

In Formula 1, A is represented by the following formula 2B, R ¹ to R is at least one ⁶ represented by the following formula 3, in R ¹ to R ^6, not ⁶ are represented by the following formula other R 3 represents ¹ to R Independently hydrogen; substituted or unsubstituted C1 to C20 alkyl; substituted or unsubstituted C1 to C20 alkoxy; substituted or unsubstituted C1 to C20 hydroxyalkyl; substituted or unsubstituted Substituted C6 to C30 aryl; substituted or unsubstituted C7 to C30 arylalkyl; substituted or unsubstituted C7 to C30 alkylaryl; or substituted or unsubstituted C2 to C30 Heteroaryl; [Formula 2b]

In formula 2b, X ¹ are the same or different from each other, and are hydrogen; substituted or unsubstituted C1 to C20 alkyl; substituted or unsubstituted C1 to C20 alkoxy; substituted or unsubstituted C1 to C20 hydroxyalkyl; substituted or unsubstituted C6 to C30 aryl; substituted or unsubstituted C7 to C30 arylalkyl; substituted or unsubstituted C7 to C30 alkylaryl; Or substituted or unsubstituted C2 to C30 heteroaryl; [Formula 3]*─Q ¹ ─Q ² ─R ⁷ ─B In formula 3, Q ¹ is O or NH; Q ² is a direct bond or CO ; R ⁷ is a direct bond or a C1 to C12 alkylene group; B is a C6 to C30 aryl group substituted by one or more hydroxyl groups; or a C7 to C30 alkylaryl group substituted by one or more hydroxyl groups. The coloring agent compound as described in item 1 of the scope of patent application, wherein B of formula 3 is represented by the following formula 4: [Formula 4]

In Formula ^{4, R a, R b, R} c, R d and R ^e in any one or more of a hydroxyl group (-OH), and the others are each independently hydrogen, C1 to C20 linear alkyl group or C3 to C20 branched alkyl. The scope of the patent application item 2 of the colorant compound, wherein, in formula 4, R ^a and R ^e are independently hydrogen; R ^c is hydroxy; R ^b and R ^d are each independently C3 to C20 branched alkyl. The coloring agent compound as described in item 3 of the scope of patent application, wherein R ^b and ^{Rd of} formula 4 are each independently a C4-branched alkyl group. The coloring agent compound according to any one of items 2 to 4 in the scope of the patent application, wherein R ⁶ of Formula 1 is represented by Formula 4. The coloring agent compound described in item 5 of the scope of patent application, wherein R ¹ to R ^{5 of} formula 1 are each independently hydrogen. The coloring agent compound according to the sixth item of the scope of patent application, wherein the compound represented by formula 1 is any one selected from the group consisting of the following compounds:

A coloring composition comprising the coloring agent compound as described in item 1 of the scope of patent application. The coloring composition as described in item 8 of the scope of patent application, including dyes And at least one of pigments. The coloring composition according to item 9 of the scope of patent application, wherein the dye and the pigment include one or more compounds showing any one of yellow, red, and green colors. The coloring composition according to item 10 of the scope of patent application, wherein the compound showing the yellow color is selected from the group consisting of metal-complex compounds, azo compounds, quinophthalone compounds, and isoindole One or more compounds in the group consisting of morpholine compounds and styryl compounds. The coloring composition according to item 10 of the scope of patent application, wherein the compound showing the red color is selected from the group consisting of metal-complex compounds, azo compounds, xanthene compounds, and diketopyrrolo One or more compounds in the group consisting of pyrrole compounds, anthraquinone compounds, and perylene compounds. The coloring composition according to item 10 of the scope of the patent application, wherein the compound showing the green color includes a group selected from the group consisting of metal-complex compounds, triarylmethane compounds, and anthraquinone compounds One or more compounds in. The coloring composition according to item 9 of the scope of patent application, wherein the pigment includes one or more selected from the group consisting of: the yellow pigment group, including PY129, PY138, PY139, PY150 and PY185; red Color groups, including PR48, PR 48:1, PR 48: 2, PR 48: 3, PR 48: 4, PR 177, PR 179, PR 207, PR 254, PR 255, PR 264 and PR 269; and green The color group includes PG 7, PG 36, PG 58 and PG 59. The coloring composition described in item 8 of the scope of patent application further includes a binder resin, a multifunctional monomer, a photoinitiator and a solvent. A color filter comprising the coloring composition as described in item 8 of the scope of patent application. A display device includes the color filter as described in item 16 of the scope of patent application.