KR20170010228A - A xanthene compound, and a colorant comprising the same - Google Patents

Abstract

A xanthene compound, a process for producing the same, and a colorant containing the same are disclosed in the present invention.

Description

[0001] The present invention relates to a xanthene compound, and a colorant containing the same. BACKGROUND ART < RTI ID = 0.0 > AXANTHENE COMPOUND, AND A COLORANT COMPRISING THE SAME &

The present invention relates to novel xanthene compounds, and processes for their preparation. The present invention also relates to a colorant composition for a color filter comprising the above compound, and a display device having such a color filter.

C.I. Acid Red 52 and the like are widely used in various industries such as various paints, water-based inks, oil-based inks, ink-jet inks, and color filters.

Color filters are widely used in various fields and are used in display devices such as a liquid crystal display (LCD) and an organic light-emitting diode (OLED) display.

Coloring compositions containing colorant materials, including pigments and / or dyes, are often used when forming color filters. Pigments generally have better stability to heat and / or the environment compared to dyes, while attainable luminance is often insufficient. On the other hand, when the dye is used as a coloring agent of a color filter, satisfactory results can be obtained in terms of brightness of the color filter, but its stability, especially heat resistance, and / or contrast ratio are often insufficient. C.I. Acid Red 52 is often used as an auxiliary colorant in color filters, especially blue and red color filters.

It is an object of the present invention to provide a novel xanthene compound. Another object of the present invention is to provide a xanthene compound exhibiting excellent thermal stability. It is another object of the present invention to provide novel xanthene compounds which can be suitably used as colorants excellent in color filter applications.

The present inventors have surprisingly found that certain compounds having two or three xanthene moieties according to the present invention exhibit excellent thermal stability, leading to the completion of the present invention. The present inventors have also found that the xanthene compounds according to the present invention can be advantageously used to form color filters.

The xanthene compound according to the present invention can achieve excellent heat resistance and can be advantageously used to form a color filter for a display.

In the present invention, "alkyl group" is understood to mean a straight chain, branched chain, or cyclic hydrocarbon group having generally 1 to 20 carbon atoms in particular. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl, tert -butyl, pentyl, neopentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

In the present invention, the "alkoxy group" specifically refers to a straight-chain, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms (Alk -O-). ≪ / RTI >

In the present invention, "aryl group" is understood to mean any functional group or substituent derived from an aromatic ring in particular. Specifically, the aryl group may have from 1 to 20 carbon atoms (particularly preferably from 6 to 12 in view of being easily synthesizable at a low cost), and some or all of the hydrogen atoms of the aryl group may have other groups, An alkoxy group, an aryl group, an aryloxy group, a thioalkoxy group, a heterocycle, an amino group, or a hydroxyl group. The aryl group is preferably an optionally substituted phenyl group, naphthyl group, anthryl group, and phenanthryl group.

In the present invention, "heterocycle" is understood to mean, in particular, a cyclic compound having at least one heteroatom as a constituent of at least one ring. Frequently used hetero atoms in the ring are sulfur, oxygen, and nitrogen. The heterocyclic compound may be saturated or unsaturated and may be aromatic or non-aromatic and may be tricyclic, tetracyclic, 5-cyclic, 6-cyclic or 7-cyclic. The heterocyclic ring compound may be further condensed with one or more other ring systems. Examples of hetero ring compounds include pyrrolidine, oxolane, thiolane, pyrrole, furan, thiophene, piperidine, oxane, thiane, pyridine, pyran, pyrazole, imidazole, Thiopyran, and derivatives thereof. The heterocyclic ring compound may optionally be unsubstituted or substituted with another group such as an alkyl group, an alkoxy group, an aryl group, a thioalkoxy group, an amino group or an aryloxy group as defined above.

In the present invention, "millbase composition" is understood to mean an intermediate composition comprising at least some of the components contained in the final composition, particularly for forming a color filter. The final composition for forming the color filter can be prepared by combining the mill base composition with other components. In the present invention, the mill base compositions often comprise one or more colorant components that are included in the final composition to form a color filter.

An aspect of the invention relates to compounds having the formula:

In Formula 1, R1 to R4 in each of the xanthene moieties may be the same or different. Each of R 1 to R 4 in each xanthene residue is independently selected from the group consisting of hydrogen, an alkyl group, and an aryl group. It is preferred that R 1 to R 4 are selected from alkyl groups. Examples of R 1 to R 4 include optionally substituted alkyl groups having 1 to 10 carbon atoms such as ethyl, propyl, isopropyl, butyl, isobutyl, sec -butyl, pentyl, hexyl, , 2-methoxyethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, and 2,2,2-trifluoroethyl group, but the present invention is not limited thereto. More preferably, R 1 to R 4 are an ethyl group. R1 and R2, or R3 and R4 may combine with each other to form a ring structure. Such ring structures may include one or more heteroatoms such as nitrogen, sulfur and oxygen. Examples of ring structures include, but are not limited to, the following structures:

In the above formula (1), R13 in each of the xanthene moieties may be the same or different. R13 in each xanthene moiety is independently selected from the group consisting of hydrogen and an alkyl group. Examples of R < 13 > include an alkyl group and hydrogen exemplified in the above R1 to R4. It is preferred that R13 is hydrogen.

In the above formula (1), "n" represents the number of xanthene residues in the compound and is thus an integer of 2 or 3. and "n" is 2.

In the present invention, L represents a linking group connecting two or three xanthene moieties which may be the same or different, respectively. L has a valence of "n" representing the number of xanthene residues in the molecule. The linking group "L" of the present invention comprises one or more aromatic rings. Examples of such aromatic rings include hydrocarbon-based aromatic rings such as benzene rings, naphthalene rings, tetralin rings, indene rings, fluorene rings, anthracene rings, phenanthrene rings, biphenyls, And five-membered rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; 6-membered rings such as pyran, pyridine, pyridazine, pyrimidine, and pyrazine; And heterocyclic aromatic rings including condensed rings such as benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, isoquinoline, acridine, quinazoline, and quinoxaline; The present invention is not limited thereto. These aromatic rings may be further substituted by substituents. Examples of such substituents include halogens such as fluorine, chlorine, and bromine, alkyl groups, carboxyl groups, and amino groups, but the present invention is not limited thereto. Preferably "L" includes a hydrocarbon-based aromatic ring having from 6 to 14 carbon atoms. More preferably "L" includes a benzene group or a naphthalene group. Especially preferably "L" is a divalent phenylene group.

The compounds of the present invention preferably have the formula (2) or (3): < EMI ID =

In the above formulas (2) and (3), each of R 1 to R 12 is independently selected from the group consisting of hydrogen, an alkyl group and an aryl group. It is preferable that R 1 to R 12 are selected from alkyl groups. Examples of R 1 to R 12 include alkyl groups mentioned as examples of R 1 to R 4 in Formula 1 above. More preferably, R 1 to R 12 are an ethyl group. R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10, or R11 and R12 may combine with each other to form a ring structure. Such ring structures may include one or more heteroatoms such as nitrogen, sulfur and oxygen. Examples of the ring structure include the ring structures referred to as examples of R 1 to R 4 in Formula 1 above.

In the general formulas (2) and (3), R13 to R15 are each independently selected from the group consisting of hydrogen and an alkyl group. Examples of R13 to R15 include alkyl groups and hydrogen mentioned above as examples of R1 to R4. It is preferable that R13 to R15 are hydrogen.

Another aspect of the invention relates to a process for preparing the xanthene compounds of the present invention. Such methods include reacting CI Acid Red 52 with one or more chlorinating agents to convert one of the sulfonic acid groups in CI Acid Red 52 to a sulfonyl chloride group and reacting the intermediate compound having sulfonyl chloride groups with one or more diamines Or triamine compound. Examples of the chlorinating agent include chlorosulfonic acid, phosphorus pentachloride, phosphorus trichloride, thionyl chloride, oxalyl chloride, and combinations thereof, but the present invention is not limited thereto. Examples of the diamine and triamine compounds include m -xylenediamine, p -xylenediamine, and 1,3,5-tris (aminomethyl) benzene trihydrochloride, but the present invention is not limited thereto.

The compounds of the present invention may be advantageously used as dyes, which may be used in combination with any one or more dyes or pigments. Accordingly, another aspect of the present invention provides a colorant material comprising a compound according to the present invention, and optionally one or more other dyes or pigments. Examples of such dyes and pigments can be found in PCT International Patent Application Publication No. WO 2012/144521 Al and Japanese Patent Application Laid-Open Publication No. JP 2014-108975 A, each of which disclosure is incorporated herein by reference in its entirety . Specifically, the compounds of the present invention can be used as colorant materials in combination with one or more blue pigments, such as epsilon-type copper phthalocyanine particles, or blue dyes such as triarylmethane compounds. In addition, the compounds of the present invention can be used as a colorant material in combination with red colorants such as quinacridone compounds and Pigment Red 254 and the like.

The compounds of the present invention can be suitably used to form color filters, particularly color filters for displays. Accordingly, a further aspect of the present invention relates to a composition for forming a culli filter comprising a compound or a colorant material according to the present invention. The composition may optionally comprise one or more components selected from the group consisting of pigments, dyes, binders, dispersing aids or dispersants, polymerizable monomers, solvents, inhibitors, polymerization initiators, and any combination thereof.

Further details of the above-mentioned ingredients, including the above pigments, dyes, binders, dispersing aid / dispersants, polymerizable monomers, solvents, inhibitors and initiators are described, for example, in PCT International Patent Application Publication No. WO 2012/144521 A, Reference may be made to the disclosure of the application publication Nos. JP 2014-108975 A and PCT International Application WO 2013/050431, the disclosures of which are incorporated herein by reference in their entirety.

In the present invention, the composition for forming a color filter may be a mill base composition for a color filter. The millbase composition preferably comprises (A) a colorant material; (B) a solvent; And (C) a binder, wherein the colorant material (A) comprises the dye compound of the present invention or the colorant material of the present invention.

The present invention also relates to a color filter comprising a compound of the invention or a colorant material. Such a color filter can be prepared by a lithographic method, in particular by the following steps: combining the components in a mill base composition according to the invention with additional components to prepare a composition for forming a color filter, applying the composition onto a substrate, Exposure, and development. The color filter can be applied to the manufacture of a display device such as a liquid crystal display device, a light emitting display device, or a solid-state image sensing device such as a charge coupled device.

The invention therefore also relates to the use of the compounds of the invention as blue or red colorants and to the use of the compounds or colorant substances of the invention in the manufacture of color filters, in particular to form blue or red portions of color filters in display devices And the use thereof.

The following examples illustrate the present invention in more detail, but the scope of the present invention should not be construed as being limited to the specific forms of the embodiments but should be construed as including obvious forms and modifications.

Example

Example 1: C.I. Conversion of Acid Red 52 to sulfonyl chloride compound 2

The above compound 1 (20 g, 34.47 mmol) was dissolved in DCM (200 ml) and the temperature was cooled to 0 占 폚. After slowly dropping oxalyl chloride (14.5 ml, 172.35 mmol), DMF (0.5 ml) was added dropwise. The temperature was raised to room temperature and stirred for 16 hours. The reaction was followed by evaporation. Toluene (20 ml) was added and then evaporated again. Diethyl ether (200 ml) was added to the mixture and stirred for 30 minutes. The resultant solid was filtered and washed with 100 ml of diethyl ether to obtain Compound (2).

Example 2: Synthesis of xanthene dendrimer compound 3

Chemical formula: C62H68N6O12S4

Molecular weight: 1217.50

p -xylenediamine (5 g, 8.61 mmol) and TEA (3.6 ml, 25.83 mmol) were dissolved in DCM (50 ml) and the temperature was cooled to 0 < 0 > C. Compound 2 (10.5 g, 18.08 mol) dissolved in DCM (30 ml) was added dropwise. The mixture was stirred at room temperature for 16 hours and concentrated under reduced pressure. The residue was treated with a SiO ₂ column (DCM: MeOH = 9: 1) to give compound 3 above.

Claims (11)

A compound of formula
≪ Formula 1 >

(here
R 1 to R 4 in each of the xanthene moieties may be the same or different and are each independently selected from the group consisting of hydrogen, an alkyl group and an aryl group;
R13 in each xanthene moiety may be the same or different and is independently selected from the group consisting of hydrogen and an alkyl group;
n is an integer of 2 or 3;
L is a linking group of "n " having at least one aromatic ring) The compound according to claim 1, wherein n is 2. 3. The compound according to claim 1 or 2, wherein L is a divalent phenylene group. A compound according to claim 1 having the formula (2) or (3):
(2)

(3)

(here
R 1 to R 12 are each independently selected from the group consisting of hydrogen, an alkyl group and an aryl group;
R13 to R15 are each independently selected from the group consisting of hydrogen and an alkyl group) 5. The compound according to claim 4, wherein R1 to R12 are an ethyl group and R13 to R15 are hydrogen. C.I. Acid Red 52 is reacted with one or more chlorinating agents to form C.I. A process according to any one of claims 1 to 5, comprising converting one of the sulfonic acid groups in Acid Red 52 to a sulfonyl chloride group and reacting the intermediate compound having the sulfonyl chloride group with at least one diamine or triamine compound Lt; RTI ID = 0.0 > a < / RTI > A colorant substance comprising a compound according to any one of claims 1 to 5 and optionally at least one further dye or pigment. A process for the preparation of the compound according to any one of claims 1 to 5 or the colorant material according to claim 7 and optionally a pigment, dye, binder, dispersant aid or dispersant, polymerizable monomer, solvent, And at least one component selected from the group consisting of any combination thereof. (A) a colorant material; (B) a solvent; And (C) a binder, wherein said colorant material (A) comprises a compound according to any one of claims 1 to 5 or a colorant material according to claim 7. . Use of the compound according to any one of claims 1 to 5 or the colorant material according to claim 7 as an auxiliary colorant for blue or red. Use of a compound according to any one of claims 1 to 5 or a colorant substance according to claim 7 in the manufacture of a color filter.