KR20170077966A - A colorant compound, and a colorant material comprising the same - Google Patents

Abstract

Disclosed herein are novel coloring compounds based on triarylmethane structures, processes for their preparation, and colorant materials comprising them.

Description

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

The present invention relates to a novel colored compound based on a triarylmethane structure, and a process for producing the same. The present invention also relates to a coloring composition for a color filter comprising the above compound, and a display device having 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 luminance of the color filter, but its stability, especially light resistance and heat resistance, and / or contrast ratio are often insufficient.

In particular, dye materials having a triarylmethane structure are excellent candidates for color filter applications, but their stability, especially light fastness and heat resistance, are not sufficient to withstand the color filter processing process (s). Also, a significant amount of triarylmethane dye is often washed out during the development process after the light irradiation process (for example, a problem of being eluted with a developing solution, etc.) in color filter processing.

An object of the present invention is to provide a compound containing a triarylmethane structure 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. It is yet another object of the present invention to provide a compound comprising a triarylmethane structure that is not substantially washed away during the development process during color filter processing. A further object of the present invention is to provide a compound comprising a triarylmethane structure having good light resistance.

The inventors have surprisingly found that the compounds according to the present invention have very excellent light 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. In addition, the present inventors have also found that the compound according to the present invention can withstand the developing process after the light irradiation process in the color filter processing.

The compounds according to the present invention can achieve excellent heat resistance and light fastness, excellent brightness and / or contrast ratio, and do not substantially wash away during the development process, and can be used very advantageously 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. 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, "alkylene group" is understood to mean a divalent radical derived from an alkyl group in particular. Typical examples of the alkylene group include - (CH ₂ ) _j - group (j is 1 to 20, preferably 1 to 10) such as methylene group (-CH ₂ -), ethylene group (-CH ₂ -CH ₂ - , And a propylene group (-CH ₂ -CH ₂ -CH ₂ -).

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, "arylene group" is understood to mean a bivalent radical derived from an aryl group in particular. A typical example of the arylene group includes a phenylene group (-C ₆ H ₄ -).

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 and R12 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, and at least one unsaturated carbon-carbon double bond (C = C) ≪ / RTI > 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. The group containing at least one unsaturated carbon-carbon double bond (C = C) but not containing an ester group preferably has the following formula (2).

(2)

-R13-R14

In the present invention, R14 is one or more unsaturated carbon-from a group, particularly a vinyl group (-CH = CH ₂₎ and -C (-ALK) = CH ₂ (wherein ALK is an alkyl group having a carbon-carbon double bond (C = C) And is in particular a methyl group), and R13 is a linking group connecting R14 to an amine group substituted in the compound of the present invention. R13 may be an alkyl- or aryl-based linking group. One or more hetero magnetic, such as O, S, NH, and N (CH ₃₎ may be inserted between CH ₂ -CH ₂ bond. Wherein said alkyl- or aryl-based linking group is selected from the group consisting of an alkylene group, a halogenated alkylene group, an arylene group, a halogenated arylene group, a heteroatom, a heteroring ring radical, a halogenated heteroring ring radical, . Exemplary types of combinations that may be R13 of the present invention include

-Alkylene-arylene-,

-Alkylene-arylene-alkylene-, and

- arylene-alkylene-arylene-

.

Specific examples of R 13 include -CH ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C ₅ H ₁₀ -, -CH ₂ -O-, -C ₂ H ₄ O-, -C ₃ H ₆ O-, -C ₂ H ₄ NH-, -C ₃ H ₆ NH-, -C ₆ H ₄ -, and -C ₁₀ H ₆ - It does not.

As a specific example of the above formula (2)

(Where n is an integer of 1 or more, preferably an integer of 1 to 18)

But the present invention is not limited thereto.

In the present invention, the group containing at least one unsaturated carbon-carbon double bond (C = C) but not containing an ester group does not include at least a (meth) acrylate group. (Meth) acrylate groups often react with a developer such as a KOH solution to hydrolyze the (meth) acrylate structure and thus can be easily washed out during the development process. Further, the heat resistance of a compound containing a (meth) acrylate group is not limited as long as the heat resistance that can be achieved by introducing a group containing the at least one unsaturated carbon-carbon double bond (C = C) It is not good.

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 each independently represent a hydrogen atom, an alkyl group, an aryl group, and a group including the unsaturated carbon-carbon double bond (C = C) ≪ / RTI > 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:

In one embodiment of the present invention, R41 to R44 are an ethyl group. In the present invention, at least one of R41 and R42 and at least one of R43 and R44 may be selected from an aryl group which may be substituted, respectively. Specific examples of the aryl group include a benzene group which may be substituted with another group. Preferably, one of R41 and R42 is selected from a benzene group which may be substituted and the other is selected from an alkyl group, one of R43 and R44 is selected from a benzene group which may be substituted and the other is selected from an alkyl group do.

In Formula 1, at least one of R41, R42, R43, R44, R11, and R12 is selected from the group including at least one unsaturated carbon-carbon double bond (C = C) but not an ester group.

Preferably, one of R < 11 > and R < 12 > is selected from the groups comprising at least one unsaturated carbon-carbon double bond (C = C) but not containing an ester group, and the other is an alkyl group which may be substituted, Lt; / RTI > Specific examples of the remaining one of R11 and R12 include an alkyl group, especially an ethyl group and a propyl group, halogenated benzenes such as fluorinated benzenes and chlorinated benzenes, alkyl-substituted benzenes, and alkoxy-substituted benzenes, The present invention is not limited thereto.

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 cation moieties, and thus is an integer of 1 or more. Between "m" and "a"

&Quot; (1) "

m = a

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 .

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, R11, R12, R21, R31 to R38, and R41 to R44 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 may be used as a colorant material in combination with a blue pigment, such as a violet pigment such as Pigment Violet 23 (PV-23) optionally including epsilon-type copper phthalocyanine particles or one or more sulfonate groups have.

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 through the following steps: combining the mill base composition according to the invention with additional components, such as photoresist (PR) material, to prepare a composition for forming a color filter, On a substrate, drying, light irradiation, and developing with a developer. During the light irradiation process, the unsaturated carbon-carbon double bonds (C = C) in the compounds of the present invention can be polymerized to form polymeric materials comprising bivalent units derived from the compounds of the present invention. Accordingly, another aspect of the present invention relates to a polymeric material comprising at least one repeating unit derived from a compound of the present invention. Such polymeric materials can be firmly fixed on the substrate and therefore are not readily washed away during the development process with a developer (e.g., a solution based on KOH). The color filter may 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 (CCD).

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)

Wherein at least one of R < 11 > and R < 12 > contains the at least one unsaturated carbon-carbon double bond (C = C) Is selected from the groups not including.

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

Compound 1

KSCN (20 g, 338.35 mmol) was dissolved in 250 ml of Acetone and then cooled to 0 占 폚. Benzoyl chloride (37.3 ml, 321.43 mmol) was added dropwise. The mixture was stirred at room temperature for 1.5 hours and then cooled to 0 占 폚. Isopropylamine (20 g, 338.35 mmol) was added dropwise thereto, followed by stirring at room temperature for 1.5 hours. The mixture was slowly added to 1500 ml of H ₂ O. The resulting solid was filtered and washed with 500 ml of H ₂ O to obtain the compound 1.

Example 1-2: Preparation of Compound 2

Compound 1 Compound 2

The compound 1 (30 g, 134.94 mmol) was dissolved in 500 ml of 2N NaOH and refluxed for 15 hours. After completion of the reaction, the reaction mixture was filtered and washed with 500 ml of H ₂ O to obtain the compound 2. [

Example 1-3: Preparation of Compound 3

Compound 2 Compound 3

After the compound 2 (9 g, 76.14 mmol) , 2- chloro-acetophenone (12.94 g, 83.75 mmol), and _{NaHCO 3 (12.79 g, 152.28 mmol} ) was dissolved in 250 ml ACN, and the mixture was stirred at 60 for 2 hours ℃ . After completion of the reaction, the temperature was lowered to room temperature. 200 ml of DCM and 200 ml of H ₂ O were added and extracted (twice). The organic layer was dried over MgSO ₄ and filtered. The mixture was concentrated under reduced pressure to obtain Compound (3).

Example 1-4: Preparation of Compound 4

Compound 3

Compound 4

The compound 4 (10.3 g, 47.17 mmol) was dissolved in 100 ml of DMF and the temperature was lowered to 0 캜. NaH (2.07 g, 52.89 mmol) was slowly added in small portions. The mixture was stirred at room temperature for 30 minutes and then dropped again to 0 占 폚. 4-vinylbenzyl chloride (6.65 ml, 47.17 mmol) was slowly added dropwise. The mixture was stirred at ambient temperature for 2 hours. After completion of the reaction, the mixture was cooled to 0 ° C and 100 ml of H ₂ O was slowly added dropwise to terminate the reaction. 300 ml of EA and 300 ml of H ₂ O were added and extracted (2 times). The organic layer was washed with H ₂ O (300 ml) (3 times). The organic layer was dried with MgSO ₄ and filtered. After concentration under reduced pressure, the resulting product was treated with a SiO ₂ column (hexane: EA = 20: 1) to obtain the above compound 4. [

Example 1-5: Preparation of Compound 5

Compound 4

Compound 5

After dissolving Compound 4 (10.7 g, 31.98 mmol) and 4,4'-bis (diethylamino) benzophenone (11.41 g, 35.18 mmol) in 250 ml of toluene (anhydrous), POCl ₃ (9 ml, 95.94 mmol ). After raising the temperature to 100 占 폚, the mixture was stirred for 15 hours. After completion of the reaction, the temperature was lowered to room temperature. The temperature was lowered to 4 ° C in an ice bath, and 100 ml of IPA was slowly added dropwise to terminate the reaction. 200 ml of H ₂ O was slowly added to the mixture, and 300 ml of DCM was added thereto for extraction (3 times). The organic layer was dried with MgSO ₄ and filtered. Concentrated under reduced pressure, and 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

Compound 5 Compound 6

The compound 5 (17.4 g, 25.68 mmol) and bis (trifluoromethane) sulfonamide lithium salt (11.05 g, 38.52 mmol) were dissolved in 250 ml of MeOH, followed by stirring at room temperature for 2 hours. The mixture was slowly added dropwise to 500 ml of H ₂ O with stirring. And extracted with 300 ml of DCM. The organic layer was dried with MgSO ₄ and filtered. The reaction mixture was concentrated under reduced pressure to obtain the above compound 6.

Example 2-1: Preparation of Compound 7

Compound 7

(12.22 ml, 99.55 mmol), bis (dibenzylideneacetone) palladium (0) (2.29 g, 3.98 mmol), 4, 5'-dichlorobenzophenone (10 g, 39.82 mmol) (2.3 g, 3.98 mmol) and potassium tert-butoxide (13.28 g, 119.46 mmol) were dissolved in 150 ml of toluene (anhydrous) Lt; / RTI > After completion of the reaction, the temperature was lowered to room temperature. The mixture was filtered through a Celite filter. The organic matter that was filtered out was added to 200 ml of DCM and 200 ml of H ₂ O to extract an organic layer. The organic layer was dried with MgSO ₄ and filtered. After concentration under reduced pressure, the resulting product was treated with a SiO ₂ column (hexane: EA = 9: 1) to obtain Compound 7.

Example 2-2: Preparation of compound 8

Compound 4 Compound 7

Compound 8

The compound 4 (3.29 g, 11.17 mmol) and the compound 7 (4.7 g, 11.17 mmol) were dissolved in 250 ml of toluene (anhydrous) and POCl ₃ (3.12 ml, 33.51 mmol) was added. After raising the temperature to 100 占 폚, the mixture was stirred for 15 hours. After completion of the reaction, the temperature was lowered to room temperature. The temperature was lowered to 4 캜 under an ice bath, and then 10 ml of IPA was slowly added dropwise to terminate the reaction. 50 ml of H ₂ O was slowly added to the mixture, and 50 ml of DCM was added thereto for extraction (3 times). The organic layer was dried with MgSO ₄ and filtered. After concentration under reduced pressure, the resulting product was treated with a SiO ₂ column (DCM: EA: MeOH = 5: 5: 1) to obtain the above compound 8.

Example 2-3: Preparation of Compound 9

Compound 8 Compound 9

The compound 8 (2.3 g, 3.13 mmol) and bis (trifluoromethane) sulfonamide lithium salt (1.35 g, 4.7 mmol) were dissolved in 30 ml of MeOH and the mixture was stirred at room temperature for 2 hours. The mixture was slowly added dropwise to 200 ml of H ₂ O with stirring. The resulting solid was filtered. Dissolving the filtered solid in DCM and extracted with 50 ml H ₂ O 50 ml. The organic layer was dried with MgSO ₄ and filtered. The mixture was concentrated under reduced pressure to obtain the above compound 9.

Example 3 (Comparative): Preparation of compound (A-I-1)

The following compound (A-I-1) was prepared according to Example 1 of Korean Patent Laid-Open Publication No. 10-2014-0026284.

Example 4 (Comparative): Preparation of a compound containing a methacrylate group

Example 4-1: Preparation of Compound 10

Compound 10

2-Hydroxyethyl methacrylate (9.32 ml, 76.84 mmol) was dissolved in 100 ml of ACN and TEA (32.13 ml, 230.52 mmol) was added. p-TsCl (21.98 g, 115.26 mmol) was dissolved in 30 ml of ACN and added dropwise. The mixture was stirred at room temperature for 3 hours. After completion of the reaction, 200 ml of H ₂ O and 200 ml of DCM were added to extract. The organic layer was washed with 1N HCl. After the organic layer was dried over MgSO ₄ and filtered. After concentration under reduced pressure, the resulting product was treated with a SiO ₂ column (Hex: EA = 5: 1 to 3: 1) to obtain Compound 10.

Example 4-2: Preparation of compound 11

Compound 3 Compound 10

Compound 11

NaH (60%) (1.37 g, 34.35 mmol) was dissolved in 50 ml of DMF and then cooled to 0 占 폚. The above compound 3 (5 g, 22.90 mmol) was slowly added. And the mixture was stirred at room temperature for 30 minutes. After the mixture was cooled to 0 占 폚, Compound 10 (9.76 g, 34.35 mmol) was slowly added thereto and stirred at room temperature. After completion of the reaction, the reaction mixture was cooled to 0 ° C, and then the mixture was slowly poured into 100 ml of H ₂ O to terminate the reaction. 100 ml of EA was added and extracted (2 times). The organic layer was washed with 100 ml H ₂ O. The organic layer was dried with MgSO ₄ and filtered. Concentration under reduced pressure was followed by SiO ₂ column treatment (Hex: EA = 18: 1) to obtain Compound 11.

Example 4-3: Preparation of Compound 12

Compound 11

Compound 12

The compound 11 (1.2 g, 3.63 mmol) and 4,4'-bis (diethylamino) benzophenone (1.76 g, 5.44 mmol) were dissolved in 30 ml of toluene (anhydrous), POCl ₃ (1.7 ml, 18.15 mmol) And 2,5-di- tert -butylhydroquinone (DTBHQ) (80 mg, 0.363 mmol). After raising the temperature to 100 DEG C, the mixture was stirred for 15 hours. After completion of the reaction, the temperature was lowered to room temperature. The temperature was lowered to 4 ° C in an ice bath, and 10 ml of IPA was slowly added dropwise to terminate the reaction. 100 ml of H ₂ O was slowly added to the mixture, and 100 ml of DCM was added thereto for extraction (3 times). The organic layer was dried with MgSO ₄ and filtered. After concentration under reduced pressure, the compound 12 was obtained by primary treatment (DCM: MeOH = 10: 1) and secondary treatment (DCM: EA: MeOH = 5: 5: 1 to 3: 3: 1) on a SiO ₂ column.

Example 4-4: Preparation of compound 13

Compound 12 Compound 13

The compound 12 (3.16 g, 4.69 mmol) and bis (trifluoromethane) sulfonamide lithium salt (2.02 g, 7.03 mmol) were dissolved in 50 ml of MeOH and the mixture was stirred at room temperature for 2 hours. The mixture was slowly added dropwise to 100 ml of H ₂ O with stirring. The resulting solid was filtered, and extracted (2 times) by the addition of 50 ml H ₂ O was dissolved in 50 ml DCM. The organic layer was washed with addition of 50 ml of H ₂ O. The organic layer was dried with MgSO ₄ and filtered. Concentration under reduced pressure gave Compound 13.

Example 5: Preparation of blue coloring composition 1

1.5 g of the compound 6 obtained in Example 1 and 13.5 g of epsilon type copper phthalocyanine particles kneaded in a blender were mixed with 6.75 g of DISPERBYK-2000 (commercially available from BYK CHEMIE), 0.2 g of dipentaerythritol hexaacryl Was charged into a bead mill along with 7.5 g of potassium carbonate and 7.50 g of potassium carbonate, 7.5 g of potassium carbonate, and 120.75 g of propylene glycol monomethyl ether acetate (PGMEA) and pulverized at 40 占 폚 for 6 to 8 hours using zirconia beads (size: 0.05 to 2 mm) To obtain a blue coloring mill base. The blue coloring mill base was mixed with a photoresist (PR) material (mill base: PR = 30 wt%: 70 wt%) to obtain a blue coloring composition 1.

Example 6: Preparation of blue coloring composition 2

Example 5 was repeated except that the compound 9 obtained in Example 2 was used instead of the compound 6 in Example 5 to obtain a blue coloring composition 2.

Example 7 (comparative example): Preparation of blue coloring composition 3

Example 5 was repeated except that the compound (A-I-1) obtained in Example 3 was used instead of the compound 6 in Example 5 to obtain a blue coloring composition 3.

Example 8 (Comparative): Preparation of blue coloring composition 4

Example 5 was repeated except that the compound containing the methacrylate group (Compound 13) obtained in Example 4 was used instead of the compound 6 in Example 5 to obtain a blue coloring composition 4.

Performance testing

(1) Production of film: The blue coloring composition was spin-coated (200 to 300 rpm for 15 seconds) on a glass substrate (EAGLE-XG FUSION GLASS; available from Corning) for forming a 2-micron thick film And prebaked at 90 DEG C for 90 seconds. Thereafter, the film was irradiated with light (UV irradiation) at an intensity of 40 mJ / cm ² for 2 seconds, and then developed with a KOH solution. The film was then post-baked at 230 캜 for 20 minutes. Subsequently, the film was irradiated (irradiated with UV) at an intensity of 400 W / m ² for 20 hours.

(2) Measurement of color and brightness: X and y color coordinates (x, y) and luminance (Y) were obtained by spectroscopically analyzing the film using an Otsuka Photal MCPD 3000 colorimeter. By comparing the values before and after the light irradiation for 20 hours,? Y,? X,? Y, and? E * ab were measured.

Light resistance test result Example ΔY Δx Δy ΔE * ab 5 (invention) 49.785 0.142 0.1713 79.162 6 (invention) -0.382 0.011 0.0229 13.994 7 (comparative example) 86.338 0.177 0.2322 118.32

(3) Elution test: The color of the film was observed before and after development using a KOH solution. The color of the films prepared from the blue coloring compositions 3 and 4 changed from deep blue to light blue after development using the KOH solution (washed out), but the color from the blue coloring compositions 1 and 2 The deep blue color of the resulting film changed little or only slightly.

As shown above, the compounds 6 and 9 according to the present invention exhibit greatly improved light resistance (ΔE * ab) compared to the compound (AI-1). In addition, contrary to washing out substantial amounts of the compound (AI-1) and the compound 13, the compounds 6 and 9 according to the present invention did not substantially wash away during the development process.

Claims (15)

A compound of formula
≪ Formula 1 >

(here
X is independently an oxygen atom, -NH-, or a sulfur atom;
R11 and R12 are each independently selected from the group consisting of a hydrogen atom, an alkyl group which may be substituted, an aryl group which may be substituted and a group which comprises at least one unsaturated carbon-carbon double bond (C = C) Selected;
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 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, and at least one unsaturated carbon-carbon double bond (C = C) Wherein R41 and R42 or R43 and R44 may combine with each other to form a ring structure;
With the proviso that at least one of R41, R42, R43, R44, R11 and R12 is selected from the group consisting of said unsaturated carbon-carbon double bond (C = C)
An is a counter-anion;
m is an integer of 1 or more; a is an integer of 1 or more, provided that they satisfy the following formula (1)
&Quot; (1) &quot;
m = a The compound according to claim 1, wherein at least one of R11 and R12 comprises a group containing the at least one unsaturated carbon-carbon double bond (C = C), but not an ester group. 3. The compound according to claim 1 or 2, wherein the group comprising at least one unsaturated carbon-carbon double bond (C = C), but not containing an ester group is at least one of the following structures.

(Where n represents an integer of 1 or more) 4. The compound according to any one of claims 1 to 3, wherein at least one of R41 and R42 and at least one of R43 and R44 are each selected from an aryl group which may be substituted. 5. The compound according to any one of claims 1 to 4, wherein X is a sulfur atom. 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, &Lt; / RTI &gt; 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)

&Lt; Formula 4 >

(here
Each X, R11, R12, R21, R31 to R38, and R41 to R44 have the same meanings as defined in claim 1) 9. A polymeric material comprising at least one repeating unit derived from a compound according to any one of claims 1 to 8. 9. A colorant substance comprising a compound according to any one of claims 1 to 8 or a polymer substance according to claim 10, and optionally at least one further dye or pigment. 10. A process for the preparation of the compound according to any one of claims 1 to 8 or the colorant material according to claim 11 and optionally a pigment, dye, binder, dispersant 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 the colorant material (A) comprises a compound according to any one of claims 1 to 8 or a colorant material according to claim 11. . Use of the compound according to any one of claims 1 to 8 or the colorant material according to claim 11 in the production of a color filter. A compound having the formula:
(3)

At least one of R < 11 > and R &lt; 12 &gt; contains the at least one unsaturated carbon-carbon double bond (C = C), but contains an ester group Selected from the non-selected groups)