TW201630895A - A compound, a method for preparing the same, and a colorant comprising the same - Google Patents

Abstract

A disclosure of the present invention includes yellow colorant compounds, methods for preparing the same, and colorants comprising the same.

Description

Compound, method of producing the same, and coloring agent containing the same

The present application claims the priority of the Korean Patent Application No. 10-2015-0010463 filed on Jan. 22, 2015, the entire disclosure of which is hereby incorporated by reference.

The present invention relates to a yellow colorant compound having excellent heat stability and a process for the preparation thereof. The present invention also relates to a coloring agent composition for a color filter comprising the compound, and a display device equipped with the color filter.

Color filters are widely used in various applications, particularly in display devices such as liquid crystal displays (LCDs) and organic light emitting displays (OLEDs). Due to the rapid advancement of such display technologies, there is a need in the art to further improve color filters, particularly in terms of brightness, contrast, and color reproducibility.

When forming a color filter, a color composition having a colorant material containing a pigment and/or a dye is often used. Pigments usually show better stability to heat and/or the environment, but are brighter than dyes. The degree is often insufficient. On the other hand, when the dye is used as a color filter colorant, satisfactory color filter brightness may be achieved, but its stability (especially light stability and thermal stability), dispersibility, and/or contrast Often insufficient.

One or more yellow colorants, such as yellow pigments and yellow dyes, are often used in the color filter as an auxiliary colorant for red or green color elements. Such a yellow colorant can be used with at least one red/green colorant and serves to alter the color exhibited by the red/green colorant alone. It is desirable in the art to develop yellow dyes that can be advantageously used in display color filter applications.

It is an object of the present invention to provide compounds which can be advantageously used as a yellow colorant for forming color filters in displays. Another object is to provide compounds that can withstand high temperature processing of color filters in display color filter applications while achieving sufficient brightness and contrast. Still another object of the present invention is to provide a compound which exhibits favorable dispersibility in a solvent used for forming a color filter in a display application.

Indeed, the inventors of the present invention have unexpectedly discovered that compounds derived from the quinacridone structure according to the present invention can exhibit excellent stability, particularly excellent photostability and thermal stability, as well as excellent dispersibility. It has also been found that the compound according to the present invention can be advantageously used as a colorant for forming a color filter having excellent brightness and contrast.

In the present invention, "alkyl" is understood to mean specifically a straight-chain, branched, or cyclic hydrocarbon group generally having from 1 to 20 carbon atoms. An example of an alkyl group Including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl Base, and cyclohexyl.

In the present invention, "aryl" is understood to specifically refer to any functional group or substituent derived from an aromatic ring. In particular, the aryl group may have 6 to 20 carbon atoms (preferably 6 to 12 due to its ease of synthesis at low cost), wherein some or all of the hydrogen atoms of the aryl group may or may not be subjected to other groups. A group, especially an alkyl, alkoxy, aryl, aryloxy, thioalkoxy, heterocyclic, amine or hydroxy group. Preferred such aryl groups are optionally substituted phenyl, naphthyl, anthracenyl and phenanthryl groups.

In the present invention, "millbase composition" is understood to specifically refer to an intermediate composition comprising at least a portion of the components to be included in the final composition for forming a color filter. The final composition for forming the color filter can be formulated by combining the paint composition with other components. In the present invention, the lacquer composition generally comprises at least a colorant component to be included in the final composition for forming a color filter.

One aspect of the invention relates to a compound having the formula (I):

In the present invention, X is independently selected from hydrogen or halogen. In the present invention, Preferably all X is hydrogen.

In the present invention, Y represents a functional group. Such a functional group can be introduced into the quinophthalone derivative compound for various purposes such as increasing stability (such as photostability and thermal stability) and/or dispersibility. In the present invention, Y is preferably a functional group selected from the group consisting of -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -COH, -C(O)NR'R", - S(O) ₂ NR'R", -NO ₂ , and -NR'R", wherein M ^{+ is} independently a cation, and R' and R" are independently selected from hydrogen, alkyl, or aryl, or R 'and R' may be joined together to form a monocyclic or polycyclic cyclic structure. Such a ring structure may contain one or more heteroatoms such as nitrogen, sulfur and oxygen. Examples of the ring structure include the following structures, but The invention is not limited to this:

Particularly when Y is -SO ₃ ^- M ⁺ , excellent results are obtained. Without wishing to be bound by any theory, excellent thermal stability and dispersibility can be obtained by introducing a -SO ₃ ^- M ⁺ group.

In the present invention, R1 to R8 represent a substituent on the structure of the phthalic anhydride. Any type of substituent can be used as long as it does not significantly interfere with the use of the compound for the final application. Preferably, R1 to R8 are independently selected from the group consisting of hydrogen, alkyl, aryl, alkyl esters (e.g., methyl esters, ethyl esters, and the like), aryl esters, and the like The functional group ("Y") explained. In the present invention, it is particularly preferred that at least one of R1 to R8 contains a large volume of an organic group. Such a large volume of organic groups can serve to increase the dispersibility of the compound in an organic solvent. And the effect of improving the thermal stability of the compound. Representative examples of such bulky organic groups include alkyl groups having at least three carbon atoms, such as propyl, isopropyl, butyl, isobutyl, secondary butyl, tert-butyl, pentyl, new A pentyl group and a hexyl group, but the invention is not limited thereto. In particular, R2 and R6 are preferably a large volume of an organic group, and R1, R3, R4, R5, R7, and R8 are hydrogen.

In the present invention, M ⁺ may be any cation. Specific examples of such a cation include protons, ammonium cations, and metal cations such as alkali metal cations (for example, Li ⁺ , Na ⁺ , K ⁺ , and the like), alkaline earth metal cations (for example, Mg ²⁺ , Ca ^{2+ )} And analogs), and a Group 13 element metal cation (for example, Al ³⁺ ). In the present invention, it is preferred to use a proton, an ammonium cation, and an alkali metal cation as M ⁺ . Alternatively, when the functional group (Y) is selected from an acidic group such as -SO ₃ ^- H ⁺ and -COO ^- H ⁺ , it may be further modified by being mismatched with a cationic compound for various purposes. This functional group.

A preferred example of such a cationic compound is a cationic polymer based dispersant. Thus, M ⁺ can be a cation of a cationic polymer based dispersant. Further improvement in thermal stability and/or dispersibility can be achieved by aligning the functional group with the cationic polymer-based dispersant. Specific examples of the cationic polymer-based dispersant include a polymer-based dispersant containing at least one ammonium group. In the present invention, the cationic polymer-based dispersant may have an average molecular weight (Mw) ranging from 4,000 g/mol to 30,000 g/mol. It is preferred in the present invention that a cationic polymer-based dispersant having a Mw of 7,000 g/mol to 25,000 g/mol can be used. Certain cationic polymer based dispersants, particularly those comprising at least one ammonium group, are available from BYK Chemical Company (BYK series).

Accordingly, yet another aspect of the invention relates to a complex comprising at least one compound of the invention and at least one cationic polymer based dispersant. This complex can be formed by mixing the colorant compound and the dispersing agent in a solvent (optionally under stirring). In the present invention, the compound of the present invention preferably comprises an anion having the following formula (I-1):

Another aspect of the invention relates to a process for the preparation of a compound of the invention.

In an embodiment of the invention, the method may comprise at least reacting at least one substituted or unsubstituted 8-quinacridine with at least one functionalizing agent. Specific examples of the substituted 8-quinacridine include 8-nitroquinidine and 8-aminoquinacridine, but the invention is not limited thereto.

In the present invention, "functionalizing agent" is understood to specifically refer to a chemical agent capable of administering a desired functional group to a target compound. In the present invention, preferred examples of the functional group include: -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -COH, -C(O)NR'R", -S(O) ₂ NR'R ", -NO ₂ , and -NR'R" (wherein M ^{+ is} independently a cation, and R' and R" are independently selected from hydrogen, alkyl, or aryl, or R' and R" may be combined A monocyclic or polycyclic cyclic structure is formed), but the invention is not limited thereto.

Any known method and functionalizing agent can be used for the process of introducing the functional group (Y) into the substituted or unsubstituted 8-quinacridine. For example, by using at least one sulfonating agent -SO ₃ ^- H ⁺ group into the 8-substituted or unsubstituted quinoline na pyridine. Examples of the sulfonating agent include sulfuric acid (including concentrated sulfuric acid and standard sulfuric acid), fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, and decyl sulfonic acid, but the present invention is not limited thereto. -COO ^- H ⁺ and -NO ₂ can be introduced by formazanization and nitration (for example, by using nitric acid), respectively. An exemplary reaction scheme for introducing several types of functional groups into the substituted 8-quinacridine is shown below, but the invention is not limited thereto:

The method for preparing a compound according to the present invention may further comprise, by imidization, a substituted or unsubstituted 8-quinacridine compound having a functional group introduced according to the above reaction with at least one functionalizing agent. At least one substituted or unsubstituted phthalic anhydride is reacted to produce a compound according to the invention. An exemplary reaction scheme is provided below, but the invention is not limited thereto.

Alternatively, it is possible to firstly substitute at least one substituted or unsubstituted phthalic anhydride with a substituted or unsubstituted 8-quinacridine to which the functional group (Y) is not introduced (especially 8-Aminoquinacridine) is reacted to produce a compound of the following formula (II), and then this compound is reacted with at least one functionalizing agent to produce a functional group (Y) suitable for the intended purpose for preparation. Method according to the compound of the invention:

In the formula (II), X and R1 to R8 each have the same meaning as defined above.

Accordingly, in a further embodiment of the invention, a process for the preparation of a compound of the invention comprises reacting at least one compound of formula (II) with at least one functionalizing agent.

The compounds or complexes of the invention may advantageously be used as yellow dyes, optionally in combination with at least one additional dye or pigment. In particular, the compounds or complexes of the invention can be used as auxiliary colorants In combination with at least one primary colorant, the primary colorant exhibits a red or green color in a display color filter application. Accordingly, another aspect of the invention provides a colorant material comprising a compound according to the invention, and optionally at least one other dye or pigment. A further further aspect of the invention provides a colorant material comprising a complex according to the invention, and optionally at least one other dye or pigment.

Examples of dyes and pigments can be found in PCT International Patent Application Publication No. WO 2012/144521 A1 and Japanese Patent Application Publication No. JP 2014-108975 A, each of which is incorporated herein in its entirety by reference. In particular, the compounds of the invention may be used as colorant materials in combination with one or more green colorants, such as halogenated metal phthalocyanine dyes or pigments (such as Pigment Green 58), or in combination with one or more red colorants, such as Pigment Red. 254. Further, the complex of the present invention can be used as a colorant material in combination with one or more green colorants, such as a halogenated metal phthalocyanine dye or pigment (such as Pigment Green 58), or in combination with one or more red colorants, such as Pigment red 254.

The compound of the present invention can be suitably used to form a color filter, particularly a color filter for display applications. Further, the complex of the present invention can be suitably used to form a color filter, particularly a color filter for display application. Accordingly, yet another aspect of the invention relates to a composition for forming a color filter comprising a compound, complex or colorant material according to the invention. The composition may further comprise at least one component selected from the group consisting of pigments, binders, dispersing aids or dispersing agents, polymerizable monomers, solvents, inhibitors, polymerization initiators, and the like Ren What combination.

Further details of the above components, including pigments, binders, dispersing aids/dispersants, polymerizable monomers, solvents, inhibitors, and initiators, can be found, for example, in WO 2012/144521 A1, JP 2014-108975 A, And the disclosure of the PCT International Patent Application Publication No. WO 2013/050431 A, the disclosure of which is hereby incorporated by reference in its entirety. In the present invention, a dispersant (specifically BYK series) commercially available from BYK Chemical Co., Ltd. and those from Otsuka Chemical Co., Ltd. (specifically TERPLUS D series) are particularly advantageous. .

In the present invention, the paint composition for a color filter specifically comprises (A) a colorant material; (B) a solvent; and (C) a dispersant, wherein the colorant material (A) comprises the compound of the present invention or A complex composition, or a color former material of the present invention.

The invention further relates to a color filter comprising a compound of the invention or a colorant material. Such a color filter can be prepared by photolithography, in particular by combining a paint composition according to the present invention with other additional components to form a composition for forming a color filter, The composition for forming the color filter is applied to the substrate, dried, exposed, and developed. The color filters can be suitably used in the preparation of display devices such as liquid crystal display devices, light-emitting display devices, or solid-state image sensing devices such as charge coupled devices (CCDs) and the like.

The invention therefore also relates to the use of the compounds or complexes of the invention as colorants, preferably as yellow colorants, and to the invention The use of a compound, complex or colorant material for the preparation of color filters, and in particular for forming green or red portions of color filters.

Another aspect of the invention relates to a compound having the formula (III):

In the formula (III), Y is a functional group as defined above, and R9 to R14 are a substituent on the structure of the quinoline main chain, and are preferably independently selected from the group consisting of hydrogen, Halogen, alkyl, aryl, alkyl ester, aryl ester, -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -COH, -C(O)NR'R", -S(O) ₂ NR'R", -NO ₂ , and -NR'R", wherein M ^{+ is} independently a cation, R' and R" are independently selected from hydrogen, alkyl, or aryl, or R' and R" may be combined Forming a monocyclic or polycyclic cyclic structure. In a particularly preferred embodiment, R14 is a methyl group and R9 is an amine group or a nitro group, and the remaining R10, R11, R12 and R13 systems in formula (III) hydrogen.

In the event that any of the patents, patent applications, and disclosures of the disclosures herein are inconsistent with the description of the present application to the extent that the term may be unclear, the description should be preferred.

The following examples are intended to describe the invention in more detail and are not intended to be limiting.

Instance Example 1: Preparation of Compound 1 by Sulfonated 8-Aminoquinacridine Intermediate

8-Nitroquinidine (1 g, 5.31 mmol) was added to H ₂ SO ₄ (2.83 mL, 53.1 mmol) and stirred at 70 ° C for 8 hours. After the reaction, the temperature was lowered to room temperature. The obtained mixture was slowly added to H ₂ O (280 mL). The precipitated material was filtered and washed with H ₂ O to obtain a sulfonated 8-nitro-quinoline na pyridine.

The sulfonated 8-nitroquinidine (1 g, 3.72 mmol) thus obtained was dissolved in EtOH (10 mL), and Fe (1.04 g, 18.63 mmol) was added. Concentrated HCl (10 mL) was added slowly. The obtained mixture was refluxed for 2 hours. Return the temperature to room temperature. Slowly introduced DCM (20mL) and saturated NaHCO ₃ (20mL) and filtered with a diatomaceous earth filter. The filtered solution was extracted. The organic layer was filtered and dried MgSO _4. After concentration under reduced pressure, a sulfonated 8-aminoquinacridine was obtained.

Benzoic acid (9.22 g, 75.54 mmol) was added to the flask and the temperature was increased to 140 °C. The sulfonated 8-aminoquinoxadine (1 g, 4.19 mmol) and 4-tributylbutyl phthalic anhydride (1.71 g, 8.39 mmol) were added and stirred for 28 hours. The temperature was lowered to room temperature and extracted with DCM (100 mL) and 2N NaOH. The organic layer was dried over MgSO ₄ and filtered with diatomaceous earth. Concentrated under reduced pressure and treated with SiO ₂ column (Hex: EA = 5: 1 to 2: 1) was treated to obtain compound 1.

Example 2: Preparation of Compound 1 by Sulfonation of Quinone Structure

8-Nitroquinidine (50 g, 256.7 mmol) was dissolved in EtOH (500 mL) and Fe (74.19 g, 1328.5 mmol) was added. Concentrated HCl (100 mL) was added slowly. The obtained mixture was refluxed for 2 hours. Return the temperature to room temperature. Slowly introduced DCM (200mL) and saturated NaHCO ₃ (200mL) and filtered with a diatomaceous earth filter. The filtered solution was extracted. The organic layer was filtered and dried MgSO _4. After concentration under reduced pressure, 8-aminoquinacridine was obtained.

Benzoic acid (97 g, 796 mmol) was added to the flask and the temperature was increased to 140 °C. 8-Aminoquinoxadine (7 g, 44.24 mmol) and 4-tributylbutyl phthalic anhydride (18.07 g, 88.5 mmol) were added and stirred for 28 hours. The temperature was lowered to room temperature and extracted with DCM (100 mL) and 2N NaOH. The organic layer was dried over MgSO ₄ and filtered with diatomaceous earth. After concentration under reduced pressure and treatment with a SiO ₂ column (Hex: EA = 5:1 to 2:1), the following intermediate compound was obtained.

The intermediate compound (1 g, 1.88 mmol) thus obtained was added to H ₂ SO ₄ (0.1 mL, 1.88 mmol), and stirred at 70 ° C for 8 hours. After the reaction, the temperature was lowered to room temperature. The obtained mixture was slowly added to H ₂ O (280 mL). The precipitated material was filtered and washed with H ₂ O to obtain Compound 1.

Example 3: Mismatch between Compound 1 and Polymer Dispersant

Compound 1 (1 g) was dissolved in MeOH (10 mL). The dispersant BYK-2000 (1 g, available from BYK Chemical Company) was dissolved in MeOH (1 mL) and slowly added to the solution of Compound 1. The mixture was stirred at room temperature for 1 hour, and was slowly added to H ₂ O (100mL). The precipitated material was filtered and washed with water and dried in a vacuum oven to obtain the compound.

Example 4: Preparation of yellow colorant paint slurry 1

3 g of the compound obtained in Example 1, 1, 4 g of TERPLUS D1160 (available from Otsuka Chemical Co., Ltd.), and 43 g of PGME were introduced into a bead mill, and zirconia beads (size: 0.05-2 mm) were used at 40 ° C. The yellow colorant lacquer 1 was obtained by grinding for 6 to 8 hours.

Example 5: Preparation of Yellow Colorant Paint 2

3 g of the compound obtained from Example 3, 4 g of TERPLUS D1160 (available from Otsuka Chemical Co., Ltd.), and 43 g of PGME was introduced into a bead mill, and was milled at 40 ° C for 6 to 8 hours using zirconia beads (size: 0.05 to 2 mm) to obtain the yellow colorant varnish 1.

Performance Testing

(1) Preparation of film: The yellow colorant lacquer was coated on a glass substrate (EAGLE-XG fused glass, available from Corning) by spin coating (200-300 rpm for 15 seconds) A film of about 2 microns thick was formed and prebaked at 90 ° C for 90 seconds. Thereafter, the film was subjected to a first post-baking at 230 ° C for 20 minutes. Subsequently, the film was subjected to a second post-baking at 230 ° C for 60 minutes. Then, the film was further subjected to light irradiation (UV irradiation) of an intensity of 400 W/m ² for 20 hours.

(2) Measurement of color and brightness: Spectroscopic methods were performed on the film by using an Otsuka Photal MCPD 3000 colorimeter to obtain x and y color coordinates (x, y) and brightness (Y). ΔE*ab was measured by comparing the respective values before and after the respective post-baking process.

(3) Measurement of contrast: Contrast was measured with a contrast tester Tsubosaka CT-1 (30,000:1) after the first post-baking process.

Claims (15)

a compound having the following formula (I), Wherein X is independently selected from hydrogen or halogen; and Y is selected from the group consisting of -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -COH, -C(O)NR'R" , -S(O) ₂ NR'R", -NO ₂ , and -NR'R", wherein M ^{+ is} independently a cation, and R' and R" are independently selected from hydrogen, alkyl, or aryl, Or R' and R" may be joined together to form a monocyclic or polycyclic cyclic structure; and R1 to R8 are independently selected from the group consisting of hydrogen, alkyl, aryl, alkyl ester, aromatic Base ester, -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -COH, -C(O)NR'R", -S(O) ₂ NR'R", -NO ₂ , and -NR'R" Wherein M ^{+ is} independently a cation, and R' and R" are independently selected from hydrogen, alkyl, or aryl, or R' and R" may be joined together to form a monocyclic or polycyclic cyclic structure. A compound of claim 1, wherein Y is -SO ₃ ^- M ⁺ . A compound according to claim 1 or 2, wherein at least one of R1 to R8 is an alkyl group having at least three carbon atoms. A compound according to any one of claims 1 to 3, which comprises an anion having the following formula (I-1): The compound of any one of claims 1 to 4, wherein the cation (M ⁺ ) is selected from the group consisting of a proton, an ammonium cation, and a metal cation. A complex of at least one compound of any one of claims 1 to 4 and at least one cationic polymer-based dispersant. A complex according to claim 6 wherein the cationic polymer-based dispersant comprises at least one ammonium group. A method for the preparation of a compound according to any one of claims 1 to 5, which comprises at least one of substituted or unsubstituted 8-quinacridine or a compound of formula (II) Reacting with at least one functionalizing agent, Wherein X and R1 to R8 each have the same meaning as described in the first item of the patent application. The method of claim 8, which comprises reacting at least one of 8-nitroquinidine or 8-aminoquinoxadine with at least one functionalizing agent. The method of claim 8 or 9, wherein the functionalizing agent is at least one sulfonating agent, and the sulfonating agent is selected from the group consisting of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, and the like. Sulfur oxide, and guanamine ruthenic acid. A color former material comprising a compound according to any one of claims 1 to 5 or a complex according to claim 6 or 7 of the patent application, and optionally at least another dye or pigment. A composition for a color filter comprising a compound according to any one of claims 1 to 5, a complex according to claim 6 or 7 of the patent application, or a claim 11 a coloring material, and optionally at least one component selected from the group consisting of a pigment, a binder, a dispersing aid or dispersing agent, a polymerizable monomer, a solvent, an inhibitor, a polymerization initiator, And any combination of them. A paint composition for a color filter comprising (A) a colorant material; (B) a solvent; and (C) a dispersant, wherein the colorant material (A) is contained in claims 1 to 5 A compound according to any one of the preceding claims, or a complexing material according to claim 6 or claim 7, or a coloring material as claimed in claim 11. A compound according to any one of claims 1 to 5, a complex according to claim 6 or 7, or a coloring material as claimed in claim 11 for preparing a display device The use of color filters. a compound having the following formula (III), Wherein Y is a functional group selected from the group consisting of -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -COH, -C(O)NR'R", -S(O) ₂ NR'R", -NO ₂ , and -NR'R", wherein M ^{+ is} independently a cation, and R' and R" are independently selected from hydrogen, alkyl, or aryl, or R' and R" may be bonded Forming a monocyclic or polycyclic cyclic structure together; and R9 to R14 are independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, alkyl ester, aryl ester, -SO ₃ ^- M ⁺ , -COO ^- M ⁺ , -COH, -C(O)NR'R", -S(O) ₂ NR'R", -NO ₂ , and -NR'R", wherein M ^{+ is} independently a cation, and R' and R" are independently selected from hydrogen, alkyl, or aryl, or R' and R" may be joined together to form a monocyclic or polycyclic cyclic structure.