KR20180020031A - Dimer-type triarylmethane dye compounds, blue resin composition comprising the same for color filter and color filter using the same - Google Patents

Abstract

The present invention relates to a blue dye compound for a color filter, and more particularly, to a novel dimer-type triarylmethane dye compound having enhanced solubility, high heat resistance, high light resistance and high brightness compared to a conventional dye, and to a blue resin composition for a color filter comprising the same and a color filter using the same. When the dimer type triarylmethane dye compound according to the present invention is used in the blue resin composition for a color filter, a dye compound which has excellent solubility in propylene glycol monomethyl ether acetate (PGMEA) used as a solvent in a process and which has high heat resistance and high brightness can be provided. Therefore, a color filter with high brightness and a high contrast ratio compared to the conventional pigment type color filter can be manufactured through the manufacture of color filters using the same.

Description

[0001] The present invention relates to a dimer type triarylmethane dye compound, a blue resin composition for a color filter comprising the same, and a color filter using the same. More particularly, the present invention relates to a dimer type triarylmethane dye compound,

The present invention relates to a blue dye compound for a color filter, and more particularly to a novel triarylmethane dye compound of dimer type having improved solubility, high heat resistance, high light resistance and high luminance as compared with conventional dyes, And a color filter using the same.

A color filter is a thin film type optical component that can realize color by extracting three colors of red, green, and blue in pixel units in a white light emitted from a light source. The color filter is a liquid crystal display (LCD) It is used for image sensor and so on.

 In a liquid crystal display, light generated from a light source passes through the liquid crystal layer, and the liquid crystal layer controls the transmittance of light. The light passing through the liquid crystal passes through the color filter layer, and a full color image is realized by adding color mixture using light passing through the color filter layer.

 An image sensor is a semiconductor module for converting an optical image into an electrical signal, and is an electronic component used for storage and transmission of a video image, and for reproducing an optical image in a display device. Therefore, it is applied to commercial apparatuses such as mobile phone cameras, digital cameras, security cameras, precision medical equipment, and household appliances.

 In general, as a method of producing a color filter, a pigment dispersion method is currently widely applied generally. This is because the color filter manufactured by the pigment dispersion method is more stable than the dye in heat resistance, light resistance, and chemical resistance due to the characteristics of the pigment. However, the pigment dispersion method has a problem in that it requires a lot of additives, a mill base, and the like in order to improve dispersion stability and particle size.

 Recently, it is a technical trend that the unit pixel size of a display and an image sensor gradually decreases according to a demand of a high resolution, high definition, high sensitivity, etc. of a display, a mobile phone, and a digital camera of a consumer. Therefore, the color filter should also be gradually smaller according to the demand of the consumer. In order to realize this, since the dispersion method through the millbase of existing pigments has a limitation in finely dividing the particles, it is necessary to achieve high brightness, high contrast ratio and high resolution by using the dye compound. However, the dye has a disadvantage that its heat resistance and light resistance are much lowered and its solubility in an ester-based organic solvent such as propylene glycol monomethyl ether acetate (PGMEA), which is a solvent used in the process, is low. Therefore, the problems of these dyes should be solved.

Japanese Patent Application Laid-Open No. 2015-134871A Korean Unexamined Patent Publication No.2015-0005139A

In order to solve the above problems, the present invention provides a dye compound for a color filter having excellent solubility in a solvent and having high heat resistance, light resistance and chemical resistance.

Further, it is another object of the present invention to provide a composition capable of forming a color filter having higher brightness and thermal stability, light stability, and chemical resistance than pigments or triarylmethane dyes currently used.

In order to solve the above problems, the present invention provides a triarylmethane blue dye compound of the following formula (A).

≪ Formula (A)

Y ^- is any one selected from the group consisting of chloride, trifluoromethanesulfonic acid and bis-trifluoromethane sulfonylimide anion, and X is a carbon number R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aromatic hydrocarbon, A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and an aromatic hydrocarbon having 6 to 10 carbon atoms.

In order to solve the above problems, the present invention provides a polymerizable dimer type triarylmethane blue dye compound represented by the following formula (B).

≪ Formula B >

Wherein X ^- is any one selected from the group consisting of chloride, trifluoromethanesulfonic acid and bis-trifluoromethane sulfonylimide anion, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, _{At least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is R ₉ represented by the following formula C, R ₁₀ represented by the following formula Is selected from R < ₁₁ > represented by the formula (E)

&Lt; EMI ID =

In the formula (C), n is an integer of 1 to 10, Y is hydrogen or methyl,

<Formula D>

In the formula (D), n is an integer of 1 to 10, Y is hydrogen or methyl,

(E)

In the formula (E), n is an integer of 1 to 10, and Y is hydrogen or methyl.

The present invention also provides a blue resin composition for a color filter comprising a dimer type triarylmethane blue dye compound and a binder resin composition represented by the formula (A) or (B).

In the blue resin composition for a color filter according to the present invention, the dimer type triarylmethane blue dye compound may be contained in an amount of 0.01 to 50% by weight based on the total weight of the blue resin composition, and if contained in the above range, Heat resistance is also excellent.

In the blue resin composition for a color filter of the present invention, the binder resin composition may include a binder resin; Reactive unsaturated compounds; A polymerization initiator; And an organic solvent.

In the blue resin composition for a color filter of the present invention, the binder resin composition may further comprise one or more other dyes in combination with a dimer type triarylmethane compound represented by the formula (A) or (B) And other dyes that are further included may be xanthene dyes, cyanine dyes, azapopyrine dyes and the like, which are generally used in color filter blue resin compositions.

In the blue resin composition for a color filter of the present invention, the binder resin composition may further comprise a blue pigment. The blue pigment may be selected from one or more of blue pigments commonly used in conventional colored resin compositions for color filters, and may include a copper phthalocyanine-based blue pigment. Examples of the copper phthalocyanine-based blue pigment include compounds classified in pigment index (published by The Society of Dyers and Colourists) as pigments. Specific examples include C.I. 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, and the like.

In the blue resin composition for a color filter of the present invention, the binder resin is not particularly limited as long as it is capable of exhibiting binding power, and a known film forming resin is useful. For example, it is possible to use a resin composition comprising a resin selected from the group consisting of carboxymethylhydroxyethylcellulose, hydroxyethylcellulose, acrylic acid resin, alkyd resin, melamine resin, epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, polyamide, polyamide- And the like.

In the blue resin composition for a color filter of the present invention, the reactive unsaturated compound may be selected from the group consisting of thermosetting monomers and oligomers, photocurable monomers and oligomers, and combinations thereof. For example, a curing agent such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, styrene and styrene derivatives, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, One polymerizable monomer, and a polymerizable monomer such as methacrylic acid, styrene, and styrene derivatives.

In the blue resin composition for a color filter of the present invention, the polymerization initiator may be selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, and a combination thereof. The photocuring initiator is preferably a compound which forms a reaction intermediate capable of inducing a polymerization reaction of the monomer and / or binder, for example, as a result of absorption of visible light or ultraviolet light. The photoinitiator may be any of those known in the art.

In the blue resin composition for a color filter of the present invention, the organic solvent is, for example, a ketone, an alkylene glycol ether, an alcohol, and an aromatic compound. Examples of the ketone group include acetone, methyl ethyl ketone, cyclohexanone, and the alkylene glycol ether group includes methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl solosorbate acetate , Ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether Triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, triethylene glycol t-butyl ether acetate, triethylene glycol methyl ether acetate, , Triethylene glycol butyl ether acetate and triethylene glycol t-butyl ether acetate. The alcohol group includes methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol and the like , And aromatic solvents include benzene, toluene, xylene, N-methyl-2-pyrrolidone and ethyl N-hydroxymethylpyrrolidone-2 acetate. Additional solvents include 1,2-propanediol diacetate, 3-methyl-3-methyl-3-methoxybutyl acetate, ethyl acetate, tetrahydrofuran and the like. These solvents may be used alone or as a mixture.

Further, the present invention provides a color filter which is manufactured by using the blue resin composition for a color filter.

When the dimer type triarylmethane dye compound according to the present invention is used in a blue resin composition for a color filter, it is possible to obtain a blue resin composition which is excellent in solubility in propylene glycol monomethyl ether acetate (PGMEA) which is a solvent used in the process and has high heat resistance and high brightness It is possible to provide a dye compound. Therefore, it is possible to manufacture a color filter with high luminance and high contrast ratio compared with the conventional pigment type color filter through the production of color filters using the same.

FIG. 1 shows absorption-transmittance measurement results of a dimer-type triarylmethane dye compound prepared according to one embodiment of the present invention.
Figure 2 shows the absorption-transmittance measurements of polymerizable dimer-type triarylmethane dye compounds prepared according to one embodiment of the present invention.
FIG. 3 shows the results of a light resistance test of a dimeric type triarylmethane dye compound prepared according to one embodiment of the present invention.
4 shows the heat resistance test results of a polymerizable dimer type triarylmethane dye compound prepared according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. In particular, the technical idea of the present invention and its core structure and action are not limited by this. In addition, the content of the present invention can be implemented by various other types of equipment, and is not limited to the embodiments and examples described herein.

Production Example 1: Synthesis of Compound 1

Compound 1 was prepared according to Reaction Scheme 1 below.

<Reaction Scheme 1>

5 g (25.9 mmol) of 4-diethylaminobenzoic acid and 50 ml of toluene were added and stirred. Thereafter, 41.4 ml of thionyl chloride was added dropwise, and the temperature was raised to 80 ° C, followed by reaction for 1 hour. After completion of the reaction, distillation under reduced pressure gave 4-diethylaminobenzoyl chloride. Dichloroethane (50 ml) was added to anhydrous aluminum chloride (4.3 g, 32.3 mmol), stirred, and 4-diethylaminobenzoyl chloride dissolved in 50 ml of dichloromethane was added dropwise while keeping the temperature below 0 캜. Thereafter, 4.23 g (25.9 mmol) of 4-diethylmethltoluidine was added dropwise, and the mixture was stirred at room temperature for 1 hour. After the completion of the reaction, water and an aqueous solution of sodium hydroxide were added to adjust the pH to 14, and the insoluble matter was removed. The organic layer was separated by layer separation and concentrated under reduced pressure to obtain 4.94 g of Compound 1 (4,4'-bisdiethylaminobenzophenone ).

Production Example 2: Synthesis of Compound 2

Compound 2 was prepared according to Reaction Scheme 2 below.

<Reaction Scheme 2>

10 g (250 mmol) of 60% sodium hydride was added to 200 ml of anhydrous tetrahydrofuran, and then 10.9 ml of 3-bromoaniline was added at 0 deg. After stirring for 30 minutes, 20.0 ml (250 mmol) of iodoethane was added dropwise at room temperature, and the mixture was reacted at room temperature for 24 hours. Water is then added to terminate the reaction and extract. The mixture was concentrated and purified by column chromatography to obtain 21.04 g of compound 2 (3-bromo-N, N-diethylaniline).

Production Example 3: Synthesis of Compound 3

Compound 3 was prepared according to the following Reaction Scheme 3.

<Reaction Scheme 3>

10 g (52.0 mmol) of 4-diethylaminobenzoic acid and 100 ml of toluene were added and stirred. Thereafter, 83.2 ml of thionyl chloride was added dropwise, and the temperature was raised to 80 ° C, followed by reaction for 1 hour. After completion of the reaction, distillation under reduced pressure gave 4-diethylaminobenzoyl chloride. Dichloroethane (100 ml) was added to anhydrous aluminum chloride (8.3 g, 62.4 mmol), and the mixture was stirred. While maintaining the temperature below 0 ° C, 4-diethylaminobenzoyl chloride dissolved in 50 ml of dichloromethane was added dropwise and stirred for 30 minutes. Thereafter, 11.9 g (52.0 mmol) of Compound 2 was added dropwise, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, water and an aqueous solution of sodium hydroxide were added to adjust the pH to 14, and the insoluble matter was removed. The organic layer was separated by layer separation and concentrated under reduced pressure to obtain 11.32 g of the compound 3 ((2-bromo- Amino) phenyl) (4- (diethylamino) phenyl) methanone).

Production Example 4: Synthesis of Compound 4

Compound 4 was prepared according to Reaction Scheme 4 below.

<Reaction Scheme 4>

7 g (175 mmol) of 60% sodium hydride was added to 150 ml of anhydrous tetrahydrofuran, and then 10 g (69.8 mmol) of 1-naphthylamine was added at 0 ° C. After stirring for 30 minutes, 14.0 ml (172 mmol) of iodoethane was added dropwise at room temperature, and the mixture was reacted at room temperature for 24 hours. Water is then added to terminate the reaction and extract. The mixture was concentrated and purified by column chromatography to obtain 11.94 g of Compound 4 (N, N-diethylnaphthalen-1-amine).

Production Example 5: Synthesis of Compound 5

Compound 5 was prepared according to Reaction Scheme 5 below.

<Reaction Scheme 5>

6.35 g (30.0 mmol) of 4-diethylaminobenzoic acid and 80 ml of toluene were added and stirred. Thereafter, 49.6 ml of thionyl chloride was added dropwise thereto, and the temperature was raised to 80 ° C, followed by reaction for 1 hour. After completion of the reaction, distillation under reduced pressure gave 4-diethylaminobenzoyl chloride. To a stirred solution of 5.17 g (38.8 mmol) of anhydrous aluminum chloride in 20 ml of dichloroethane was added 4-diethylaminobenzoyl chloride dissolved in 50 ml of dichloromethane while maintaining the temperature below 0 ° C, and the mixture was stirred for 30 minutes. Then, 6.2 g (30.0 mmol) of Compound 4 was added dropwise, and the mixture was stirred at room temperature for 1 hour. After the completion of the reaction, water and an aqueous solution of sodium hydroxide were added to adjust the pH to 14, and the insoluble matter was removed. The organic layer was separated by layer separation and concentrated under reduced pressure to obtain 7.47 g of compound 5 ((4-diethylamino) Yl) (4- (diethylamino) phenyl) methanone)) was obtained.

Manufacturing example  6: Synthesis of Compound 6

 Compound 6 was prepared according to Reaction Scheme 6 below.

<Reaction Scheme 6>

0.48 g (1.48 mmol) of 4,4'-bisdiethylaminobenzophenone was dissolved in 10 ml of toluene, 0.54 ml of phosphorus chloride was added thereto, and the mixture was stirred at room temperature. Then, 0.2 g of 1,1'-dinaphthylamine ) Was added and refluxed. After the completion of the reaction, the reaction mixture was cooled to room temperature, separated from the reaction mixture, and concentrated under reduced pressure. The obtained compound was purified to obtain 0.52 g of Compound 6.

Production Example 7: Synthesis of Compound 7

 Compound 7 was prepared according to Reaction Scheme 7 below.

<Reaction Scheme 7>

0.5 g of Compound 6 (0.52 mmol) was dissolved in 50 ml of methanol, and 0.17 g (1.14 mmol) of trifluoromethanesulfonic acid was added to the solution to replace the salt. After completion of the reaction, the reaction mixture was separated, and then concentrated under reduced pressure to obtain 0.3 g of Compound 7.

Production Example 8: Synthesis of Compound 8

Compound 8 was prepared according to the following Reaction Scheme 8.

<Reaction Scheme 8>

 After 0.5 g of Compound 6 (0.52 mmol) was dissolved in 50 ml of methanol, 0.32 g (1.14 mmol) of lithium bis (trifluoromethanesulfonyl) imide was added to replace the salt. After completion of the reaction, the reaction mixture was separated by layer and concentrated under reduced pressure to obtain 0.3 g of Compound 8.

Production Example 9: Synthesis of Compound 9

<Reaction Scheme 9>

1.12 g (3.33 mmol) of Compound 1 was dissolved in 30 ml of toluene, and 1.55 ml of phosphorus chloride was added. After stirring at room temperature, 0.3 g (1.11 mmol) of 1,1'-dinaphthylamine was added and refluxed. After completion of the reaction, the reaction mixture was cooled to room temperature. After layer separation, the reaction mixture was concentrated under reduced pressure. The obtained solid was dissolved in 50 ml of methanol, and 2.1 g (7.33 mmol) of lithium bis (trifluoromethanesulfonyl) . After completion of the reaction, the reaction mixture was separated by layer and concentrated under reduced pressure to obtain 0.38 g of Compound 9.

Production Example 10: Synthesis of Compound 10

<Reaction formula 10>

1.34 g (3.33 mmol) of Compound 3 was dissolved in 30 ml of toluene, and 1.55 ml of phosphorus chloride was added. After stirring at room temperature, 0.3 g (1.11 mmol) of 1,1'-dinaphthylamine was added and refluxed. After completion of the reaction, the reaction mixture was cooled to room temperature. After layer separation, the reaction mixture was concentrated under reduced pressure. The obtained solid was dissolved in 50 ml of methanol, and 2.1 g (7.33 mmol) of lithium bis (trifluoromethanesulfonyl) . After the completion of the reaction, the mixture was separated and concentrated under reduced pressure to obtain 0.22 g of Compound 10.

Preparation Example 11: Synthesis of Compound 11

<Reaction Scheme 11>

1.04 g (2.78 mmol) of Compound 5 was dissolved in 30 ml of toluene, 1.30 ml of phosphorus chloride was added, and the mixture was stirred at room temperature. Then, 0.3 g (1.11 mmol) of 1,1'-dinaphthylamine was further added and refluxed. After completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure. The resulting solid was dissolved in 50 ml of methanol, and lithium bis (trifluoromethanesulfonyl) imide (1.76 g, 6.12 mmol) . After completion of the reaction, the reaction mixture was separated and then concentrated under reduced pressure to obtain 0.22 g of Compound 11.

Comparative Example: Compound 12

The following compounds 12 (Victoria pure blue BO from Aldrich, CAS No. 2390-60-5) were used as comparative examples.

Preparation Example 12: Synthesis of Compound 13

Compound 13 was prepared according to Reaction Scheme 12 below.

<Reaction Scheme 12>

1.0 g (4.58 mmol) of 4,4'-difluorobenzophenone was added to 6.74 g (6.42 mmol) of diethanolamine and reacted at 160 ° C. After completion of the reaction, the mixture was cooled to room temperature and the layers were separated. The mixture in the water layer was subjected to column and vacuum distillation to obtain 1.42 g of Compound 13.

Production Example 13: Synthesis of Compound 14

 Compound 14 was prepared according to Reaction Scheme 13 below.

<Reaction Scheme 13>

1 g of compound 13 (2.57 mmol) is dissolved in 100 ml of methylene chloride, and then 1.25 g (12.3 mmol) of triethylamine is added thereto. Then, 1.89 g (12.3 mmol) of methacrylic anhydride is added and reacted at 40 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, separated from the reaction mixture, and concentrated under reduced pressure to obtain 1.27 g of Compound 14.

Production Example 14: Synthesis of Compound 15

<Reaction Scheme 14>

 1.47 g (2.22 mmol) of Compound 14 was dissolved in 10 ml of toluene, 1.03 ml of phosphorus chloride was added thereto, and the mixture was stirred at room temperature. Then, 0.2 g (0.74 mmol) of 1,1'-dinaphthylamine was further added and refluxed. After completion of the reaction, the reaction mixture was cooled to room temperature. After the layers were separated, the reaction mixture was concentrated under reduced pressure. The resulting solid was dissolved in 50 ml of methanol, and 2.2 equivalents of lithium bis (trifluoromethanesulfonyl) imide was added thereto to replace the salt. After completion of the reaction, the reaction mixture was separated, and then concentrated under reduced pressure to obtain 0.41 g of Compound 15.

Experimental Example 1: Measurement of absorption and permeability

Compounds 6 to 11 prepared according to one embodiment of the present invention were compared with the comparative example 12 for absorption and permeability. For the measurement method, a dye compound was applied to a glass substrate using a spin coater. This was measured using a Shimadzu UV-3600, and the results are shown in Fig.

As can be seen from FIG. 1, the novel triarylmethane novel blue dye compounds synthesized in accordance with one embodiment of the present invention were synthesized in a blue color range of 425 nm to 450 nm in the same manner as the conventional blue dye compound (Comparative Example 12) The dye compound of the present invention can be used as a blue dye composition for a color filter.

Also, the absorption and permeability of Compound 6, Compound 8, and Compound 15 prepared according to one embodiment of the present invention were compared.

As can be seen from FIG. 2, the novel triarylmethane novel blue dye compound synthesized in accordance with one embodiment of the present invention exhibits transmission at 425 nm to 450 nm, which is a blue region. Therefore, It can be seen that it can be used as a blue dye composition.

Experimental Example 2; Light resistance measurement

Compounds 6 to 11 and Compound 12, which were prepared according to one embodiment of the present invention, were measured using a UV exposure apparatus of Model 66902 of DRIEL instruments with an output power of 500 W. First, the dye is spin-coated with 0.5 wt% of the film, and the degree of color fading according to the exposure time to the UV exposure apparatus is measured by using a UV spectrometer to measure the absorption at the maximum wavelength Respectively. The degree of color fading was then calculated by the following equation 1, and the results are shown in FIG. 3 and Table 1. FIG.

<Formula 1>

division Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 DR 35.71 37.45 21.82 33.04 1.89 7.48 47.44

As shown in Table 1 and FIG. 3, the novel triarylmethane blue dye compounds of the dimer type synthesized according to one embodiment of the present invention are superior in color to the conventional blue dye compound 12 (Comparative Example) It is confirmed that the degree of desirability is improved by 1.3 times to 6.3 times. Therefore, it can be seen that the dye compound of the present invention has better light resistance than the conventional ones.

Experimental Example 3: Measurement of heat resistance

 Compounds 6 to 11, Compound 15 and Comparative Example 12 prepared according to one embodiment of the present invention were measured using a TA instrument Thermogravimetric Analyzer Q500. The sample was heated at a rate of 10 ° C / min in a nitrogen atmosphere to compare the heat resistance of the sample with the temperature at which the compound decomposed into the substance (a portion where the mass% of 5% was reduced). The results are shown in Table 2 below.

division Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 15 Temperature 72.3 DEG C 238.0 DEG C 241.7 DEG C 248.0 DEG C 275.0 DEG C 243.9 DEG C 62.9 ° C 283.5 DEG C

 As shown in Table 2, the compound according to one embodiment of the present invention can decompose the compound at a higher temperature than that of the compound 12 of the comparative example. In particular, the compound 10 and the compound 15 can stand at a very high temperature. Therefore, it can be seen that the dye compound according to the present invention has excellent heat resistance.

In addition, the compound according to one embodiment of the present invention increased the decomposition temperature of the compound 8 by about 170 ° C, and the compound 15 in which the acrylate group was introduced was increased by about 40 ° C compared to the compound 8, . Through this, it can be seen that the introduction of the salt group and the acrylate group greatly improves the thermal stability of the dye. It is also understood that it can be used as a blue compound for a color filter because it satisfies a temperature condition of 230 deg. C or more, which is a temperature condition required in a color filter process.

Experimental Example 4: Measurement of solubility

Dye compounds of Compound 6 to Compound 11, Compound 15, and Compound 12 of Compound 12 prepared according to one embodiment of the present invention were dissolved in propylene glycol monomethyl ether acetate (PGMEA) as a solvent and subjected to sonication and centrifugation After removing the supernatant through a microfilter, the weight of the filtrate before removing the solvent and the weight after removing the solvent were calculated to obtain the results shown in Table 3 below.

division Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 15 PGMEA
Solubility
(wt%)
3.11
0.83
6.41
4.87
5.08
4.50
0.03
> 8

 As shown in [Table 3], it can be confirmed that Compound 12 (Comparative Example), which is a conventional blue dye, has a very poor solubility in propylene glycol monomethyl ether acetate (PGMEA). On the other hand, it was confirmed that the solubility of the dimer type triarylmethane novel dye compounds developed through the present invention was greatly increased. Thus, the blue dye compound according to the present invention exhibits a solubility of 3 wt% or more, which is significantly improved compared to the conventional dye for an ester organic solvent such as propylene glycol monomethyl ether acetate (PGMEA).

Experimental Example  5: Preparation of blue resin composition for color filter and measurement of physical properties

(1) Preparation of a blue resin composition for a color filter

A photosensitive blue resin composition was prepared in the following composition.

(a) Binder resin: 4 g of a copolymer of benzyl methacrylate (BzMA) / methacrylic acid (MAA) / RMA (Mw = 17,000)

(b) Additive: acrylic monomer, heat polymerization inhibitor (MEHQ) 0.5 g

(c) Blue dye compound: 1.5 g

(d) Photopolymerization initiator: Oxime ester-based high sensitivity PI OXE-57 2 g

(e) Solvent: Propylene glycol monomethyl ether acetate 84 g

(2) Measurement of heat resistance of a blue resin composition for a color filter

For measurement of the heat resistance, the blue resin composition for a color filter prepared in the above-mentioned Examples and Comparative Examples was spin-coated at 1000 rpm for 10 seconds on a glass substrate of 2.5 cm x 2.5 cm and then pre-baked on a hot plate at 100 캜 for 1 minute and 40 seconds (pre-bake), and then exposed using an exposure apparatus at an exposure dose of 60 mJ / cm 2 (based on 365 nm). Then, color characteristics were confirmed using a spectrophotometer, Lambda 1050 manufactured by Perkin Elmer Co., and the color characteristics were confirmed. After the heat treatment was further performed in a 230 ° C convection oven for 1 hour, Results were obtained.

division Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 15 ΔEab * 4.77 15.95 5.30 11.12 15.49 10.58 23.47 10.22

As shown in Table 4, Compound 12 (Comparative Example), which is a conventional blue dye, was found to have a very poor ΔEab * value of 23.47 when a blue resin composition for a color filter was produced. On the other hand, it was confirmed that the ΔEab * value of the heat resistance measurement of the dimer type triarylmethane novel dye compounds developed through the present invention was increased by 8 to 18.7.

(3) Chemical resistance measurement of blue resin composition for color filter

For measurement of the heat resistance, the blue resin composition for a color filter prepared in the above-mentioned Examples and Comparative Examples was spin-coated at 1000 rpm for 10 seconds on a glass substrate of 2.5 cm x 2.5 cm and then pre-baked on a hot plate at 100 캜 for 1 minute and 40 seconds (pre-bake), and then exposed using an exposure apparatus at an exposure dose of 60 mJ / cm 2 (based on 365 nm). Then, after post-baking in a convection oven at 230 ° C for 20 minutes, color characteristics were confirmed by using a spectrophotometer, Lambda 1050 manufactured by Perkin Elmer, and dipped in each solvent (IPA, PGMEA, cyclohexanone) for 10 minutes. The color characteristics were checked to obtain a value of [Delta] Eab *, and the results of Table 5 were obtained.

division Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 15
ΔEab * IPA 0.51 0.22 2.29 0.35 0.21 0.13 1.59 PGMEA 0.72 0.61 16.76 4.59 5.30 1.19 0.67 Cyclohexanone 0.91 0.52 21.11 6.30 6.11 2.00 2.26

As shown in Table 5, it was confirmed that the ΔEab * value of the dimer type triarylmethane novel dye compounds developed through the present invention, which is a result of the chemical resistance measurement, there was.

Claims (10)

A triarylmethane blue dye compound of the dimer type represented by the following formula (A)
&Lt; Formula (A)

Y ^- is any one selected from the group consisting of chloride, trifluoromethanesulfonic acid and bis-trifluoromethane sulfonylimide anion, and X is a carbon number R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aromatic hydrocarbon, A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and an aromatic hydrocarbon having 6 to 10 carbon atoms. A triarylmethane blue dye compound of the polymerizable dimer type represented by the following formula (B): < EMI ID =
&Lt; Formula B &gt;

Wherein X ^- is any one selected from the group consisting of chloride, trifluoromethanesulfonic acid and bis-trifluoromethane sulfonylimide anion, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, _{At least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is R ₉ represented by the following formula C, R ₁₀ represented by the following formula Is selected from R &lt; ₁₁ &gt; represented by the formula (E)
&Lt; EMI ID =

In the formula (C), n is an integer of 1 to 10, Y is hydrogen or methyl,
<Formula D>

In the formula (D), n is an integer of 1 to 10, Y is hydrogen or methyl,
(E)

In the formula (E), n is an integer of 1 to 10, and Y is hydrogen or methyl. A dimeric triarylmethane blue dye compound according to claim 1 or 2; And
A blue resin composition for a color filter, comprising a binder resin composition. The method of claim 3,
Wherein the dimer type triarylmethane blue dye compound is contained in an amount of 0.01 to 50 wt% based on the total weight of the blue resin composition. The method of claim 3,
The binder resin composition comprises a binder resin; Reactive unsaturated compounds; A polymerization initiator; And an organic solvent. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method of claim 5,
Wherein the binder resin composition further comprises at least one dye selected from xanthene dyes, cyanine dyes, and azapphyrin dyes. The method of claim 5,
Wherein the binder resin composition further comprises a copper phthalocyanine blue pigment. The method of claim 5,
The binder resin may be at least one selected from the group consisting of carboxymethylhydroxyethylcellulose, hydroxyethylcellulose, acrylic acid resin, alkyd resin, melamine resin, epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, polyamide, polyamide- Wherein the color filter resin is at least one selected from the group consisting of polyvinyl alcohol and polyvinyl alcohol. The method of claim 5,
Wherein the reactive unsaturated compound is selected from the group consisting of a thermosetting monomer or oligomer, a photo-curable monomer or oligomer, and a combination thereof, and the polymerization initiator is selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, and a combination thereof A blue resin composition for a color filter. A color filter produced by using the blue resin composition for a color filter according to claim 3.

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