KR101380942B1 - Triarylmethane dye compounds, colored resin composition comprising the same for color filter and color filter using the same - Google Patents

Abstract

[화학식 2]

The present invention relates to a blue dye compound for a color filter, characterized in that the triarylmethane blue dye compound represented by the following [Formula 1] or [Formula 2], a blue resin containing a blue dye compound according to the present invention The composition is characterized by excellent solubility in organic solvents such as propylene glycol methyl ether acetate (PGMEA), excellent mixing with other pigments, high brightness, and high heat resistance. It is possible.
[Chemical Formula 1]

(2)

Description

Triarylmethane blue dye compound, blue resin composition for color filter comprising same, and color filter using same {triarylmethane dye compounds, colored resin composition comprising the same for color filter and color filter using the same}

The present invention relates to a blue dye compound for color filters, and more particularly, to a novel triarylmethane dye compound having improved solubility, high heat resistance and high luminance compared to conventional dyes, and a blue resin composition for color filters including the same. And a color filter using the same.

Liquid crystal displays display images using the optical and electrical properties of the materials of the liquid crystal invention. The liquid crystal display device has advantages such as light weight, low power, low driving voltage and the like as compared with a CRT, a plasma display panel and the like. A liquid crystal display device includes a liquid crystal layer disposed between glass substrates. Light generated from the 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.

Dyeing methods, printing methods, electrodeposition methods, and pigment dispersion methods are generally known as methods for producing color filters used in liquid crystal display devices, and methods using dyes from the past have been studied. However, when dyes are used, heat resistance, Chemical resistance and the like are lower than those of pigments, so that it is difficult to apply. In addition, pigment dispersion method is generally applied because dyeing method is not economical because of complicated process. Pigment has a lower transparency than dyes but has been overcome by advances in pigment refinement and dispersion techniques. Since the color filter fabricated by the pigment dispersion method is pigment stable, it is stable to light, heat, solvent, etc., and when patterning by photolithography, it is easy to produce a color filter for a large screen and a high-precision color display, have.

Pigments used in the pigment-disperse color resists include red, green, and blue pigments, respectively, when forming an RGB color filter, and in general, yellow pigments, purple pigments, and the like may be further included in order to express colors more effectively. . In a method of producing a color filter by the pigment dispersion method, a color resist solution is first applied on a substrate with a spin coater and dried to form a coating film. Then, colored pixels are obtained by pattern exposure and development of a coated film, heat treatment is performed at a high temperature to obtain a first color pattern, and this operation is repeated according to the number of colors to produce a color filter. The most important factor that determines the performance of a color resist is the property of the pigment used as a colorant and its dispersibility and dispersed state. In recent years, along with the enlargement of the LCD and the high definition, the required characteristics of the color filter such as high transmittance of the colored layer, high contrast ratio, narrowing of the black matrix width and high reliability are increasing every year. Up to now, as a means for satisfying these requirements, the color characteristics such as brightness and contrast ratio have been satisfied by making the pigment as fine as possible.

However, in order to prepare a pigment dispersion, the pigment powder obtained by synthesis cannot be used as it is, in order to facilitate stable dispersion and miniaturization, and a pigmentation process such as salt milling is required, and such a post-treatment process is undesirable in terms of environmental protection. In addition, many additives such as dispersants and pigment derivatives are required to stabilize the dispersion state, and production is possible only after a very difficult and cumbersome manufacturing process. And pigment dispersions require rigid storage and transport conditions to maintain optimal quality conditions.

In the case of the pigment dispersion, the pigment is present in the form of particles and not only the light is scattered but also the surface area of the pigment is rapidly increased due to the fineness of the pigment, and due to the uneven pigment particle generation due to the deterioration of the dispersion stability, There is a difficulty in.

In addition, various studies have recently been conducted to achieve high brightness, high contrast ratio and high resolution using pigments. However, due to problems such as pigment refinement and dispersion stability mentioned above, the properties of the color filter using a pigment as a colorant The improvement is insignificant.

As an alternative, studies have been made to improve the luminance and contrast ratio using a hybrid type colorant which improves physical properties by mixing pigments and dyes. Through this, a certain level of luminance and contrast ratio has been improved. However, , The effect of improving the physical properties is not so significant.

Recently, in order to solve such problems and achieve high brightness, high contrast ratio and high resolution, it has been studied to use dyes instead of pigments as colorants. Many attempts have been made using triarylmethane dye as a blue colorant. In general, the triarylmethane dye has a high permeability to 420-450 of the color filter, but the solubility in the solvent used in the color composition for the color filter is inferior, and heat resistance is poor. Generally, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and the like are generally used as a solvent for use in a coloring composition for a color filter, , The solubility in cyclohexanone is easy to ensure, but the solubility in PGMEA or PGME is low. However, in the case of cyclohexanone, it is necessary to use a dye having high solubility for PGMEA or PGME as the use thereof as an environmentally harmful substance is prohibited.

As one of several studies of existing triarylmethane dyes, mention is made of salt compounds of naphthalenesulfonic acid and naphthylaminesulfonic acid anions in triarylmethane dye cations to improve solubility and heat resistance, and colored resin compositions and color filters including the same. It is. However, these compounds have a low solubility in propylene glycol monomethyl ether acetate (PGMEA) and the like and have a problem of low heat resistance.

As another example, triarylmethane cations and anions of other dyes have been studied, but these compounds have some problems in that their solubility in an ester organic solvent such as PGMEA is lowered, although their heat resistance is partially improved.

Therefore, the problem to be solved by the present invention is to solve the above problems, to secure the brightness and contrast ratio, etc. superior to the pigment and to solve the problems such as heat resistance of the conventional triaryl methane dyes having a level of heat resistance equivalent to the pigment It is to provide a blue dye compound.

The present invention also provides a blue resin composition for a color filter comprising the blue dye compound and a color filter using the blue resin composition.

In order to solve the above problems,

It provides a triarylmethane blue dye compound represented by the following [Formula 1].

[Chemical Formula 1]

In the above formula (1)

X ^- is trifluoromethanesulfonic acid or bistrifluorotansulfonimide anion,

The R ₁ , R ₂ , R ₃ And R ₄ are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and R ₅ represented by the following [Formula 1]: ,

The R ₁ , R ₂ , R ₃ And R ₄ At least one of R ₅ includes:

N is an integer of 1 to 10,

R ₅ is represented by the following [formula 1].

In the above formula 1,

M is an integer of 1 to 10, and R ₆ is hydrogen or methyl.

In addition, the present invention provides a triarylmethane blue dye compound represented by the following [Formula 2] to solve the above problems.

(2)

In the above formula (2)

X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,

R ₇ , R ₈ , R ₉ And each R ₁₀ is independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and any one selected from R ₁₁ represented by the following [Formula 2]: ,

R ₇ , R ₈ , R ₉ And R ₁₀ At least one of R ₁₁ includes:

N is an integer of 1 to 10,

R ₁₁ is represented by the following [Formula 2].

[Structural formula 2]

In the above formula 2,

M is an integer of 0 to 10, and R ₁₂ is hydrogen or methyl.

Further, in order to solve the above problems,

Blue dye compounds; Binder resin; Reactive unsaturated compounds; A polymerization initiator; Organic solvent; And additives;

The blue dye compound provides a blue resin composition for a color filter, characterized in that the compound represented by the above [Formula 1] or [Formula 2].

According to an embodiment of the present invention, the blue dye compound may further include at least one selected from xanthene dye, cyanine dye, and azapopyrine dye together with the compound of [Formula 1] or [Formula 2]. Can be.

According to another embodiment of the present invention, the blue dye compound may be 0.01% by weight to 50% by weight relative to the total weight of the blue resin composition.

The blue resin composition for a color filter according to the present invention may further comprise a blue pigment, if necessary, and the blue pigment may be a copper phthalocyanine blue pigment.

According to another embodiment of the present invention, the reactive unsaturated compound is a thermosetting monomer or oligomer; Photocurable monomers or oligomers; And a combination thereof.

According to another embodiment of the present invention, the polymerization initiator may be selected from the group consisting of a thermosetting initiator, a photocuring initiator and a combination thereof.

Further, in order to solve the above problems,

It provides a color filter, which is produced using the blue resin composition for the color filter.

The triarylmethane blue dye compound according to the present invention has excellent solubility, high heat resistance and high brightness property to propylene glycol monomethyl ether acetate (PGMEA). Therefore, when using the triarylmethane blue dye compound according to the present invention, it is possible to produce a color filter of high brightness, high contrast ratio compared to the color filter using a conventional pigment.

1 is spin-coated on a glass substrate of 10 cm × 10 cm for Examples 1 to 4 and Comparative Examples 1 and 2, pre-bake for 3 minutes on a hot plate at 90 ℃ and at room temperature After cooling for 1 minute, the light was exposed at an exposure dose of 100 mJ / cm 2 (365 nm standard) using an exposure machine, and then subjected to postbake at 220 ° C. for 30 minutes, and then the transmittance graph according to the wavelength ( UV-vis-spectrum).

Hereinafter, the present invention will be described in more detail.

Recently, various colorants have been developed as colorants for color filters. However, in order to satisfy both high transmittance and solubility, heat resistance and high brightness for organic solvents at the same time, the particle size of particles or the particle size of particles may be high. The development of highly durable dyes that are very small below the nanometer is urgently needed, but satisfying and reliable dyes are rare.

The blue dye compound according to the present invention is excellent in solubility, heat resistance, high brightness and the like, and is suitable as a blue composition for color filters.

The blue dye compound according to the present invention may be a blue dye compound represented by the following [Formula 1].

[Chemical Formula 1]

In the above formula (1)

X ^- is trifluoromethanesulfonic acid or bistrifluorotansulfonimide anion,

The R ₁ , R ₂ , R ₃ And R ₄ are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and R ₅ represented by the following [Formula 1]: ,

The R ₁ , R ₂ , R ₃ And R ₄ At least one of R ₅ includes:

N is an integer of 1 to 10,

R ₅ is represented by the following [formula 1].

In the above formula 1,

M is an integer of 1 to 10, and R ₆ is hydrogen or methyl.

In addition, the blue dye compound according to the present invention may be a blue dye compound represented by the following [Formula 2].

(2)

In the above formula (2)

X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,

R ₇ , R ₈ , R ₉ And each R ₁₀ is independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and any one selected from R ₁₁ represented by the following [Formula 2]: ,

R ₇ , R ₈ , R ₉ And R ₁₀ At least one of R ₁₁ includes:

N is an integer of 1 to 10,

R ₁₁ is represented by the following [Formula 2].

[Structural formula 2]

In the above formula 2,

M is an integer of 0 to 10, and R ₁₂ is hydrogen or methyl.

The blue resin composition for a color filter according to the embodiment of the present invention may include the blue dye compound, a binder resin, a reactive unsaturated compound, a polymerization initiator, an organic solvent, and an additive, and may further include a blue pigment, if necessary. have.

The blue dye compound may optionally further include one or more other dyes together with the compound according to [Formula 1] or [Formula 2], and other dyes to be additionally included are generally used in color filter blue resin compositions. Aciden dyes, cyanine dyes, azapophyrin dyes and the like.

The blue dye compound optionally comprising at least one other dye together with the compound according to [Formula 1] or [Formula 2] may be included in 0.01% to 50% by weight relative to the total weight of the blue resin composition, the blue dye compound When it is contained in the above range, it is excellent in solubility in solvents, has high brightness, and is excellent in heat resistance.

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. Color Index Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60 and the like.

The blue resin composition for a color filter may express high brightness by using a compound dye of [Chemical Formula 1] or [Chemical Formula 2] according to the present invention having excellent transmittance at 420 nm to 450 nm.

The binder resin is not particularly limited as long as it is a resin capable of exhibiting binding force, and particularly known film forming resins are useful.

For example, cellulose resins such as carboxymethylhydroxyethylcellulose and hydroxyethylcellulose, acrylic acid resin, alkyd resin, melamine resin, epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, polyamide, polyamide- A binder such as polyimide and the like are useful.

In addition, useful binders include resins having photopolymerizable unsaturated bonds, for example, acrylic acid resin. In particular, homopolymers and copolymers of polymerizable monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, styrene and styrene derivatives, methacrylic acid, itaconic acid, maleic acid, Copolymers between polymerizable monomers, such as anhydrides, monoalkyl maleates, containing caryobut groups, and polymeric monomers, such as methacrylic acid, styrene and styrene derivatives, are useful.

Examples thereof include compounds containing an oxirane ring and an ethylenically unsaturated compound, such as glycidyl (meth) acrylate, acryloylglycidyl ether, monoalkylglycidyl itaconate, and the like, and carboxyl- Containing polymer compound and a compound containing a hydroxyl group and an ethylenically unsaturated compound (unsaturated alcohol) (for example, allyl alcohol, 2-buten-4-ol, oleyl alcohol, 2-hydroxyethyl (Meth) acrylate, N-methylol acrylamide, and the like and a carboxyl-containing polymer compound. Such a binder may contain an unsaturated compound having no isocyanate group.

The equivalent of the unsaturation of the binder (molecular weight of the binder per unsaturated compound) may generally range from 200 to 3,000, in particular from 230 to 1,000, in order to provide adequate photopolymerization as well as film hardness. The acid value is generally 20 to 300, in particular 40 to 200, to provide sufficient alkali developability after film exposure. The average molecular weight of the binder is preferably 1,500 to 200,000, especially 10,000 to 50,000 g / mol.

The reactive unsaturated compound may be selected from the group consisting of a thermosetting monomer or an oligomer, a photo-curable monomer or oligomer, and a combination thereof. Preferably, the reactive unsaturated compound may be the photo-curable monomer. The reactive unsaturated compound may have one or more reactive double bond Group.

Useful photocurable monomers in this context are, in particular, reactive solvents or reactive diluents, for example mono-, di-, tri- and multifunctional acrylates and methacrylates, vinyl ethers, glycidyl ethers and the like. Additional reactive groups include aryl, hydroxyl, phosphate, urethane, secondary amines, N-alkoxymethyl groups and the like.

Monomers of this kind are known in the art and are described, for example, in Roempp, Lexikon, Lacke und Druckfarben, Dr. Ulrich Zorll, Thimem Verlag Stuttgart-New York, 1998, p 491/492. The choice of monomer depends in particular on the type and intensity of irradiation used, the desired reaction by the photoinitiator and the film properties. These photocurable monomers can also be used individually or in combination of monomers.

The polymerization initiator may be a thermosetting initiator, a photocuring initiator or a combination thereof, preferably a photocuring initiator, and such photocuring initiator may be a result of absorption of visible or ultraviolet light, for example, the monomer and / or A compound that forms a reaction intermediate capable of inducing a polymerization reaction of a binder. Photoinitiators or are known in the art and are described, for example, in Roempp, Lexikon, Lacke und Druckfarben, Dr. Ulrich Zorll, Thimem Verlag Stuttgart-New York, 1998, p 445/446.

Such organic solvents are, for example, ketones, alkylene glycol ethers, alcohols and aromatic compounds. The ketone group includes acetone, methyl ethyl ketone, cyclohexanone and the like, and the alkylene glycol ether group includes methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), and methyl solosorbe 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 Tere acetate, diethylene glycol butyl ether acetate, diethylene glycol t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, triethylene Glycol, triethylene glycol butyl ether acetate, triethylene glycol t-butyl ether acetate, and the like, and the alcohol group includes methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxy butanol, and the like. The aromatic solvent group includes benzene, toluene, xylene, N-methyl-2-pyrrolidone, ethyl N-hydroxymethylpyrrolidone-2 acetate and the like. Further other solvents include 1,2-propanediol diacetate, 3-methyl-3-methyl-3methoxybutyl acetate, ethyl acetate, tetrahydrofuran and the like. These solvents can be used alone or in mixtures.

Such additional additives may be used without limitation as long as they meet the respective purposes. As a preferable example, fatty acids, fatty amines, alcohols, bean oil, wax, rosin, resins, benzotriazole derivatives and the like can be used for improving the surface texture. More preferably, the fatty acid may be stearic acid or behenic acid, and the fatty amine may be stearylamine or the like.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It will be clear to those who have knowledge.

<Examples>

Synthesis Example 1. Synthesis of Compound Represented by Formula 3

(1) Synthesis of Compound of Formula (I)

A compound represented by [Formula I] was synthesized according to [Scheme 1].

[Reaction Scheme 1]

(I)

To a bis N-ethyl, 28.52 g (80.00 mmol) of N-hydroxyethylaminobenzophenone and 17.80 g (176.00 mmol) of triethylamine, 300 mL of dichloromethane was added and dissolved. Thereafter, 27.13 g (176.00 mmol) of methacrylic anhydride was added, and the temperature was raised to 40 ° C and maintained. After the reaction was completed, water was added, the layers were separated, and 20 mL of saturated sodium chloride solution was added thereto, followed by stirring for 30 minutes. After layer separation, the organic layer was dried under reduced pressure and purified to obtain 32.71 g (66.40 mmol) of [Formula I].

(2) Synthesis of Compound

A compound represented by [Formula II] was synthesized according to [Scheme 2].

[Reaction Scheme 2]

[Formula I] [Formula II]

32.71 g (66.40 mmol) was added to 500 mL of chloroform and stirred. Thereafter, 50.91 g (332.00 mmol) of phosphorus oxychloride was added and stirred for 15 minutes. 14.96 g (66.40 mmol) of N-cyclohexyl-1-naphthylamine were added and then refluxed. After completion of the reaction, the mixture was cooled to room temperature, water was added, and then stirred. After layer separation, the mixture was concentrated under reduced pressure and the obtained compound was purified to obtain 30.62 g (41.58 mmol) of [Formula II].

(3) Synthesis of Compound Represented by Formula 3

A compound represented by [Formula 3] was synthesized according to the following [Scheme 3].

[Reaction Scheme 3]

[Formula II] [Formula 3]

After dissolving 100 mL of methanol in 10.00 g (13.58 mmol), 2.57 g (14.94 mmol) of sodium trifluoromethanesulfonate was added to a 20% aqueous solution to dissolve the salt. After filtration, the obtained compound was dissolved in chloroform, washed with water and concentrated under reduced pressure to obtain 7.42 g (8.73 mmol).

Synthesis Example 2 Synthesis of Compound Represented by Formula 4

A compound represented by [Formula 4] was synthesized according to the following [Scheme 4].

[Reaction Scheme 4]

[Formula II] [Formula 4]

After dissolving 100 mL of methanol to 10.00 g (13.58 mmol), 4.29 g (14.94 mmol) of lithium bistrifluoromethanesunfonimide was added to a 20% aqueous solution to replace the salt. After filtration, the obtained compound was dissolved in chloroform, washed with water and concentrated under reduced pressure to obtain 9.86 g (10.05 mmol).

Synthesis Example 3 Synthesis of Compound Represented by Formula 5

(1) Synthesis of Compound

A compound represented by [Chemical Formula III] was synthesized according to [Scheme 5].

[Reaction Scheme 5]

[Formula (III)

50 mL of dichloromethane was added to 53.09 g (220.00 mmol) of N- (4-hydroxycyclohexyl) -1-naphthylamine and 24.49 g (242.00 mmol) of triethylamine, followed by stirring. Thereafter, 37.31 g (242.00 mmol) of methacrylic anhydride were added, and the temperature was raised to 40 ° C and maintained. After completion of the reaction, water was added and the layers were separated, 20 mL of a saturated sodium chloride solution was added, and the mixture was stirred for 30 minutes. After layer separation, the organic layer was dried under reduced pressure and purified to give 58.92 g (190.43 mmol).

(2) Synthesis of Compound

The compound represented by [Formula IV] was synthesized according to [Scheme 6].

[Reaction Scheme 6]

[Formula III] [Formula IV]

61.79 g (190.43 mmol) of bis-N, N-diethylaminobenzophenone and 1000 mL of chloroform were added and stirred. Thereafter, 145.99 g (952.15 mmol) of phosphorous oxychloride was added and stirred for 15 minutes. 58.92 g (190.43 mmol) was added, and the mixture was refluxed. After completion of the reaction, the mixture was cooled to room temperature, water was added, and the mixture was stirred. After layer separation, the mixture was concentrated under reduced pressure and the obtained compound was purified to obtain 85.84 g (131.59 mmol).

(3) Synthesis of Compound Represented by Formula 5

A compound represented by [Formula 5] was synthesized according to the following [Scheme 7].

[Reaction Scheme 7]

[Formula IV] [Formula 5]

After dissolving 20.00 g (30.66 mmol) of methanol in 300 mL, 5.80 g (33.73 mmol) of sodium trifluoromethanesulfonate was added to a 20% aqueous solution to replace the salt. After filtration, the obtained compound was dissolved in chloroform, washed with water and concentrated under reduced pressure to obtain 17.05 g (22.26 mmol).

Synthesis Example 4. Synthesis of Compound Represented by Formula 6

A compound represented by [Formula 6] was synthesized according to the following [Scheme 8].

[Reaction Scheme 8]

[Formula IV] [Formula 6]

After dissolving 20.00 g (30.66 mmol) of methanol in 300 mL, 9.68 g (33.73 mmol) of lithium bistrifluoromethanesunponimide was added to a 20% aqueous solution to replace the salt. After filtration, the obtained compound was dissolved in chloroform, washed with water and concentrated under reduced pressure to obtain 21.01 g (23.42 mmol).

Comparative Example

A compound represented by [Formula V] was synthesized according to [Scheme 9].

[Reaction Scheme 9]

[Formula V]

After dissolving 5.00 g (9.72 mmol) of Basic Blue 7 in 50 mL of methanol, 2.08 g (10.69 mmol) of p-toluenesulfonic acid sodium salt was added to a 20% aqueous solution to dissolve the salt. After filtration, the obtained compound was dissolved in chloroform, washed with water and concentrated under reduced pressure to obtain 2.80 g (4.31 mmol) of Chemical Formula V.

Experimental Example 1. Solubility Evaluation

The blue dye compounds according to Synthesis Examples 1 to 4 and Comparative Example 1 were dissolved in PGMEA to confirm their solubility, and the results are shown in the following [Table 1].

division Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Comparative Example PGMEA > 3% > 10% > 3% > 10% <1%

As shown in [Table 1], it can be confirmed that the blue dye compound has a high solubility of 10% or more in PGMEA in Synthesis Examples 2 and 4, and in Synthesis Examples 1 and 3, it is confirmed to show solubility of 3% or more in PGMEA. It became. It was confirmed that the compound of the comparative example showed relatively low solubility as compared with the compound of the example. Therefore, the blue dye compound according to the present invention has excellent solubility in organic solvents.

Example 1: Preparation of blue resin composition for color filter

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

(a) Binder Resin: A copolymer of benzyl methacrylate / methacrylic acid (60: 40 mass ratio) (Mw = 20000) 2.7 g

(b) Acrylic monomer: dipentaerythritol hexaacrylate 10 g

(c) Blue dye compound: Synthesis Example 1 2.3 g

(d) Photopolymerization initiator: 2 g of Irgaeure OXE-01 manufactured by BASF

(e) Solvent: Propylene glycol monomethyl ether acetate 83 g

Example 2: Preparation of blue resin composition for color filter

A photosensitive blue resin composition was prepared in the same manner as in Example 1 except that 2.3 g of the compound of Synthesis Example 2 was used as a blue dye compound.

Example 3: Preparation of blue resin composition for color filter

A photosensitive blue resin composition was prepared in the same manner as in Example 1, except that 2.3 g of a compound of Synthesis Example 3 was used as a blue dye compound.

Example 4: Preparation of a blue resin composition for a color filter

A photosensitive blue resin composition was prepared in the same manner as in Example 1, except that 2.3 g of a compound of Synthesis Example 4 was used as a blue dye compound.

Comparative Example 1

A photosensitive blue resin composition was prepared in the same manner as in Example 1, except that CI blue pigment 15: 6 1.65 g and CI purple pigment 23 0.65 g were used instead of the blue dye compound.

Comparative Example 2

A photosensitive blue resin composition was prepared in the same manner as in the composition of Example 1, except that 2.3 g of the compound of Formula V of the comparative example was added instead of the blue dye compound.

Experimental Example 2. Measurement of transmittance graph, luminance and contrast ratio

Hot coating at 90 ° C. by spin coating the blue resin compositions for color filters prepared in Examples 1 to 4 and Comparative Examples 1 and 2 to 2 μm thickness on a 10 cm × 10 cm glass substrate to measure brightness and contrast ratio. Pre-bake was performed for 3 minutes at and then cooled at room temperature for 1 minute. This was exposed at an exposure amount (365 nm standard) of 100 mJ / cm 2 using an exposure machine.

Thereafter, postbake was performed for 30 minutes in a convection oven at 220 ° C., and then luminance was measured using a spectrophotometer MCPD3700 manufactured by Otsuka electronic Inc., and CT-1 using Tsubosaka Corporation. Contrast ratio was measured. The transmission spectrum is shown in FIG. 1, and the results of luminance and contrast measurement are shown in the following [Table 2].

division x y Luminance Contrast ratio Example 1 0.1457 0.113 14.63 14274 Example 2 0.1436 0.113 14.80 15512 Example 3 0.1419 0.113 15.82 14538 Example 4 0.1400 0.113 16.27 15195 Comparative Example 1 0.1366 0.113 13.70 11210 Comparative Example 2 0.1531 0.113 7.81 4032

As shown in FIG. 1, in Comparative Example 2, it was confirmed that the heat resistance was very poor and the transmittance was not good at 420-450 nm. It can be seen that the transmittance graphs of Examples 1 to 4 are higher in transmittance at 420-450 nm than in Comparative Example 1 using a pigment, and particularly, in Example 4, a high transmittance of 94% or more is shown.

In addition, as shown in [Table 2], it can be seen that the luminance is high when the transmittance of 420-450 nm is high in the transmittance graph of FIG. 1.

In the case of Comparative Example 2, the lowest transmittance at 420-450 nm showed the lowest luminance, and the luminance of Examples 1 to 4 was higher than that of Comparative Example 1 using the pigment. In particular, in the case of Example 4, it can be seen that the luminance is 18% or more higher than that of Comparative Example 1 using the pigment.

In the case of the contrast ratio, it can be seen that the results of Examples 1 to 4 are higher than those of Comparative Example 1 using the pigment.

Experimental Example 3. Measurement of heat resistance

In order to measure heat resistance, the blue resin compositions for color filters prepared in Examples and Comparative Examples were spin-coated at two thicknesses on a glass substrate of 10 cm × 10 cm, respectively, and prebaked for 3 minutes on a hot plate at 90 ° C. bake), and then cooled at room temperature for 1 minute. This was exposed at an exposure amount (365 nm standard) of 100 mJ / cm 2 using an exposure machine.

Thereafter, postbake was performed for 30 minutes in a convection oven at 220.degree. After the heat treatment was performed, the color characteristics were again determined, and ΔEab * values were obtained.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 ΔEab * 2.72 2.49 2.91 2.68 2.27 31.69

Generally, it is known that satisfies the reliability because it satisfies ΔEab * 3 or less.

In Examples 1 to 4, it can be seen that the reliability is satisfied by ΔEab * 3 or less. In Comparative Example 1, the pigment itself has high heat resistance and satisfies ΔEab * 3 or less, and in Comparative Example 2, it can be seen that heat resistance is largely inferior.

Claims (11)

delete Triarylmethane blue dye compound represented by the following [Formula 2]:
(2)

In [Formula 2],
X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,
R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms,
N is an integer of 1 to 10, wherein R ₁₁ is represented by the following [formula 2],
[Structural formula 2]

In [Formula 2], m is an integer of 0 to 10, and R ₁₂ is hydrogen or methyl. delete 3. The method of claim 2,
[Formula 2] is a triarylmethane blue dye compound, characterized in that the compound represented by the following [Formula 5] or [Formula 6]:
[Chemical Formula 5]

[Chemical Formula 6]

Blue dye compounds; Binder resin; Reactive unsaturated compounds; A polymerization initiator; Organic solvent; And additives;
The blue dye compound is a blue dye composition for a color filter, characterized in that the blue dye compound represented by the above [Formula 2] according to claim 2. 6. The method of claim 5,
Wherein the blue dye compound further comprises at least one selected from xanthene dyes, cyanine dyes, and azapopyrine dyes. 6. The method of claim 5,
Wherein the blue dye compound is 0.01% by weight to 50% by weight based on the total weight of the blue resin composition. 6. The method of claim 5,
Wherein the blue resin composition may further comprise a blue pigment, and the blue pigment is a copper phthalocyanine blue pigment. 6. The method of claim 5,
The reactive unsaturated compound may be a thermosetting monomer or oligomer; Photocurable monomers or oligomers; And a combination thereof. &Lt; / RTI &gt; 6. The method of claim 5,
Wherein the polymerization initiator is selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, and a combination thereof. The color filter manufactured using the blue resin composition for color filters of any one of Claims 5-10.

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