KR20170010969A - A colorant compound, and a colorant material comprising the same - Google Patents

Abstract

The present invention relates to a novel coloring compound having a triarylmethane substructure, a production method thereof, and a colorant material comprising the same. The coloring compound has excellent thermal resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring compound,

The present invention relates to novel coloring compounds based on triarylmethane substructures, and to a process for their preparation. The present invention also relates to a coloring composition for a color filter comprising the same, and a display device provided with such a color filter.

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. Due to the rapid development of display technology, there is a need in the industry for further improvements in color filter technology, especially in terms of brightness, contrast ratio, and color reproducibility.

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.

In particular, dye materials having a triarylmethane structure are not good candidates for color filter applications, but their stability, especially heat resistance, is insufficient to withstand the high temperature process (s) during color filter processing. PCT International Patent Application Publication No. WO 2004/144521 Al discloses a coloring dispersion, a colored resin composition used for a color filter, a color filter formed using a colored resin composition used for the color filter, And a liquid crystal display device and an organic light emitting diode display device including the color filter. In particular, the publication discloses a colored dispersion comprising a colorant of a dimerized triarylmethane structure having the formula:

It is an object of the present invention to provide a novel compound comprising a triarylmethane substructure having excellent heat resistance. Another object of the present invention is to provide a coloring compound, in particular a blue coloring compound, which is capable of exhibiting sufficient brightness and / or contrast ratio while also being able to withstand high temperature processes in color filter processing in display applications.

The present inventors have surprisingly found that the compounds according to the present invention have very excellent heat resistance. The present inventors have also found that the compounds according to the present invention can be advantageously used to form color filters having excellent brightness and / or contrast ratio.

The compounds according to the present invention can achieve excellent heat resistance and excellent luminance and / or contrast ratio, and can be very advantageously used for forming 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. Some or all of the hydrogen atoms of the alkyl group may be substituted or unsubstituted by other groups, especially a halogen atom, an amino group or a hydroxyl group.

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, "halogenated" is understood to mean in particular that at least one of the hydrogen atoms of the modifying chemical is replaced by a halogen atom, preferably fluorine and chlorine, more preferably fluorine. When all of the hydrogen atoms are replaced with halogen atoms, the halogenated chemical is said to be perhalogenated. For example, "halogenated alkyl group" is (per) fluorinated alkyl group, for example (per) fluorinated methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec - butyl, or tert - butyl; And for example, -CF _3, -C ₂ F _5, heptafluoroisopropyl _{(-CF (CF 3) 2)} , hexafluoro isopropyl (-CH (CF _{3) 2),} or -CF ₂ (CF _{2) 4} CF ₃ and the like.

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.

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

In the present invention, X is independently an oxygen atom, -NH-, or a sulfur atom. Particularly, X is preferably a sulfur atom.

In the present invention, R11 is independently selected from the group consisting of a hydrogen atom, an alkyl group, and an aryl group. The alkyl group and the aryl group may be substituted with another group. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group may be substituted with one or more halogen atoms, especially a fluorine atom, or an amino group. The aryl group may be substituted with at least one halogen atom (e.g., a fluorine atom), optionally an alkyl group having 1 to 4 fluorinated carbon atoms, and a hydroxyl group. Preferably, R11 is independently selected from an alkyl group or an aryl group substituted with a halogen atom. Specific examples of R < 11 > include halogenated benzenes (e.g., fluorinated benzene and chlorinated benzene), alkyl-substituted benzene, and alkoxy-substituted benzene, but the present invention is not limited thereto.

In the present invention, R21 is independently selected from the group consisting of a hydrogen atom, an alkyl group, and an aryl group. The alkyl group and the aryl group may be substituted with another group. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group may be substituted with one or more halogen atoms, especially a fluorine atom, or an amino group. The aryl group may be substituted with at least one halogen atom (e.g., a fluorine atom), optionally an alkyl group having 1 to 4 fluorinated carbon atoms, and a hydroxyl group. Preferably, R21 is independently selected from an alkyl group or an aryl group substituted with a halogen atom. Specific examples of R21 include halogenated benzenes (e.g., fluorinated benzene and chlorinated benzene), alkyl-substituted benzene, and alkoxy-substituted benzene, but the present invention is not limited thereto.

In the present invention, R31, R32, R33, R34, R35, R36, R37 and R38 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, a sulfonyl group, ≪ / RTI > The alkyl group and the alkoxy group may be substituted with another group. R34 and R35 is -O-, -NH-, -S-, or -SO ² combine with each other - may be formed. Preferably, R31 to R38 are hydrogen atoms.

In the present invention, R41, R42, R43, and R44 are each independently selected from the group consisting of a hydrogen atom, an alkyl group, and an aryl group. The alkyl group and the aryl group may be substituted with another group. Examples of these include alkyl groups having 1 to 10 carbon atoms which are optionally substituted, 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. Fluorine-containing groups, particularly alkyl groups or aryl groups substituted with one or more fluorine atoms, can be used in the present invention. Each of R41 and R42, or R43 and R44 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:

R41 to R44 are preferably an ethyl group.

In the present invention, L means a linking group connecting two or more identical or different triarylmethane substructures. L represents the valence of "n ", which is understood to represent the number of triarylmethane substructures in the molecule. In the present invention, the linking group "L" comprises at least one aromatic ring. These aromatic rings may be further substituted with substituents. The nitrogen atom in the amine group of the heterogeneous ring compound substructure in Formula 1 may be connected to any atom in the substituent of the aromatic ring of L or may be directly connected to an atom constituting the aromatic ring included in L. Examples of the aromatic ring include hydrocarbon-based aromatic rings such as a benzene ring, a naphthalene ring, a tetralin ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, 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 a substituent include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, an alkyl group, a carboxyl group, and an amino group, 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 a benzene group. Specific examples of "L" include the following structures, but the present invention is not limited thereto:

In the present invention, "n" means the number of triarylmethane substructures, and thus is an integer of 2 or more. The "n" is often 4 or less, more preferably 3 or less. Particularly preferably, "n"

In the present invention, "a" means the valency of the counter-anion "An" "a" may be an integer of 1. "a" is preferably an integer of 2 or more, more preferably 2 or 3, most preferably 2.

In the present invention, "m" means the number of cationic moieties, "b" means the number of anion moieties, and therefore each is an integer of 1 or more. "m" and "b" can be appropriately selected depending on the number ("n") of cationic triarylmethane substructures and the number of counter anions ("a"). Between "n "," m ", "a ", and" b "

&Quot; (1) "

n x m = a x b

In the present invention, "An" means any counter-anion. The kind of the counter-anion is not particularly limited in the present invention, and it may be an organic anion or an inorganic anion. An example of the counter-anion can be found in Japanese Patent Application Laid-Open Publication No. JP 2014-108975 A, the disclosure of which is incorporated herein by reference in its entirety. In the present invention, An ^a- is preferably selected from the group consisting of halides, a borate anion, a carboxylate anion, a sulfate anion, a sulfonate anion, a sulfonimide anion, a phosphate anion, Is selected. Particularly preferred in the present invention is an anionic compound comprising at least one sulfonate group, especially at least two sulfonate groups. In one embodiment of the invention, the counter-anion (An) comprises an anionic dye or pigment compound comprising at least one anionic functional group such as a carboxylate group, a sulfate group, a phosphate group, and a sulfonate group . Examples of the 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. Without wishing to be bound by any particular theory, it is understood that by selecting the anionic dye or pigment compound as the counter-anion (An), the heat resistance of the compound of the present invention can be improved at least by its molecular weight increase .

The compounds of the present invention preferably include divalent cations having the formula (2-1) or (2-2): < EMI ID =

≪ Formula (2-1)

≪ Formula (2-2)

In the formulas (2-1) and (2-2), each of X, R11, R21, R31 to R38, and R41 to R44 has the same meaning as defined above.

In the present invention, R51, R52, R53 and R54 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, a sulfonyl group and a hydroxyl group. The alkyl group and the aryl group may be substituted with another group. Examples of these include alkyl groups having 1 to 10 carbon atoms which are optionally substituted, 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.

Another aspect of the invention relates to a process for the preparation of the compounds of the invention. This process comprises reacting a compound of formula 3 and a compound of formula 4:

In the general formulas (3) and (4), X, L, R11, R21, R31 to R38, R41 to R44 and "n" have the same meanings as defined above. If desired, the desired counter-anion can be introduced.

The following examples can be referred to for more specific details regarding the method for producing the above compound.

The compounds of the present invention may be advantageously used as blue colorants, which may optionally be used in combination with 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 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 Publication No. JP 2014-108975 A, each of which is incorporated herein by reference in its entirety. Specifically, the compounds of the present invention can be used as colorant materials in combination with blue pigments, such as epsilon-type copper phthalocyanine particles or violet pigments such as Pigment Violet 23 (PV-23) optionally comprising one or more sulfonate groups .

The compounds of the present invention can be suitably used to form color filters. 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 a compound of the present invention or a colorant material.

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.

Accordingly, the present invention also relates to the use of the compounds of the invention as colorants, preferably as blue colorants, and to the use of the compounds or colorant materials of the invention in the production of color filters, Lt; / RTI >

Another aspect of the present invention relates to compounds having the formula:

(3)

In Formula 3, each of X, L, R11, R21, and "n" has the same meaning as defined above.

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 1-1: Preparation of Compound 1

α, α'-dibromo-ρ-xylene (5 g, 18.65 mmol) and o-toluidine (4.2 g, 39.18 mmol) were dissolved in 250 ml of acetone and stirred at 50 ° C. After completion of the reaction, 100 ml of H ₂ O and 100 ml of DCM were added and extracted. The organic layer is dried over MgSO ₄ and filtered. After concentration under reduced pressure, the residue was treated with a SiO ₂ column (Hex: EA = 40: 1) to obtain the compound 1.

Example 1-2: Preparation of Compound 2

Potassium thiocyanate (3.37 g, 34.76 mmol) was dissolved in 300 ml of acetone and the temperature was cooled to 0 < 0 > C. Benzoyl chloride (3.67 ml, 31.6 mmol) was added dropwise. The mixture was stirred at room temperature for 1.5 hours and then cooled to 0 < 0 > C again. The compound 1 (10 g, 31.6 mmol) was dissolved in 30 ml of acetone and added dropwise. And the mixture was stirred at room temperature for 2 hours. After completion of the reaction, 200 ml of H ₂ O was added. 200 ml of EA was added and extracted twice. The organic layer is dried over MgSO ₄ and filtered. The reaction mixture was concentrated under reduced pressure to obtain Compound (2).

Example 1-3: Preparation of Compound 3

The above compound 2 (15 g, 23.33 mmol) was dissolved in 150 ml of 2N NaOH and refluxed for 15 hours. After completion of the reaction, the temperature was cooled to room temperature. 150 ml of DCM was added and the mixture was extracted twice. The organic layer is dried over MgSO ₄ and filtered. The mixture was concentrated under reduced pressure to obtain the above compound 3.

Example 1-4: Preparation of Compound 4

The compound 3 (5 g, 11.5 mmol), 2-chloroacetophenone (1.78 g, 11.5 mmol) and sodium bicarbonate (2.41 g, 28.75 mmol) were dissolved in 100 ml of ACN and the temperature was raised to 60 ° C . After stirring for 3 hours, the temperature was cooled to room temperature. 100 ml of DCM and 200 ml of H ₂ O were added and extracted. The organic layer is dried over MgSO ₄ and filtered. After concentrating under reduced pressure, the residue was treated with a SiO ₂ column (Hex: EA = 40: 1) to obtain the compound 4.

Example 1-5: Preparation of Compound 5

The compound 4 (7 g, 11.02 mmol) and 4,4'-bis (diethylamino) benzophenone (3.93 g, 12.12 mmol) were dissolved in 150 ml of anhydrous toluene and POCl ₃ (5.13 ml, 55.1 mmol) . The temperature was raised to 100 占 폚 and stirred for 15 hours. After completion of the reaction, the temperature was cooled to room temperature. The temperature was further reduced to 4 < 0 > C in a cooling bath and 10 ml of IPA was slowly added dropwise to quench. 50 ml of H ₂ O was slowly added and 100 ml of DCM was added and extracted three times. The organic layer is dried over MgSO ₄ and filtered. After concentration under reduced pressure, the residue was treated with a SiO ₂ column (DCM: EA: MeOH = 5: 5: 1) to obtain the above compound 5.

Example 1-6: Preparation of Compound 6

The compound 5 (5 g, 3.78 mmol) and bis (trifluoromethane) sulfonimide lithium salt (2.71 g, 9.46 mmol) were dissolved in 100 ml of MeOH and stirred at room temperature for 2 hours. 500 ml of H ₂ O was slowly added dropwise to the mixture under stirring. The product solids were filtered and washed three times with 50 ml of H ₂ O to give compound 6.

Claims (14)

A compound of formula
≪ Formula 1 >

(here
X is independently an oxygen atom, -NH-, or a sulfur atom;
R11 is independently selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, and an optionally substituted aryl group;
R21 is independently selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, and an optionally substituted aryl group;
R31, R32, R33, R34, R35, R36, R37, and R38 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, cyano group, nitro group, sulfonyl group, Gt; is selected from the group consisting of < RTI ID = 0.0 >
R41, R42, R43 and R44 are each independently selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group, and an optionally substituted aryl group, wherein R41 and R42 or R43 and R44 are bonded to each other to form a ring structure ≪ / RTI >
L is a linking group of "n " comprising at least one aromatic ring;
An is a counter-anion;
n is an integer of 2 or more; m is an integer of 1 or more; a is an integer of 1 or more; b is an integer of 1 or more, provided that they satisfy the following formula (1)
&Quot; (1) "
n x m = a x b
2. The compound of claim 1, wherein L comprises a benzene group. The compound according to any one of claims 1 to 3, which comprises a divalent cation of the following general formula (2-1) or (2-2).
≪ Formula (2-1)

≪ Formula (2-2)

(here
Each X, R11, R21, R31 to R38, and R41 to R44 have the same meanings as in claim 1;
R51, R52, R53 and R54 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, a cyano group, a nitro group, a sulfonyl group and a hydroxyl group ) 4. The compound according to any one of claims 1 to 3, wherein X is a sulfur atom. 5. The compound according to any one of claims 1 to 4, wherein R < 11 > is an aryl group which may be substituted. 6. The compound according to any one of claims 1 to 5, wherein R21 is an aryl group which may be substituted. 7. Compounds of formula I according to any one of claims 1 to 6, wherein An ^a- comprises a halide, a borate anion, a carboxylate anion, a sulfate anion, a sulfonate anion, a sulfonimide anion, a phosphate anion, ≪ / RTI > The method according to according to any hanhang of claim 7, wherein the anion An is ^a- comprising a least one sulfonate compound is a compound. 9. A process for preparing a compound according to any one of claims 1 to 8, comprising reacting a compound of formula (3) and a compound of formula
(3)

≪ Formula 4 >

(here
Each X, L, R11, R21, R31 to R38, R41 to R44, and n have the same meaning as defined in claim 1) 9. A colorant substance comprising a compound according to any one of claims 1 to 8 and optionally at least one further dye or pigment. 9. A process for the preparation of the compound according to any one of claims 1 to 8 or the colorant material according to claim 10 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 8 or a colorant material according to claim 10. . Use of a compound according to any one of claims 1 to 8 or a colorant substance according to claim 10 in the production of a color filter. A compound having the formula:
(3)

(here
Each X, L, R11, R21, and n have the same meaning as defined in claim 1)