WO2013176383A1

WO2013176383A1 - Triarylmethane blue dye compound, blue resin composition for color filter including same, and color filter using same

Info

Publication number: WO2013176383A1
Application number: PCT/KR2013/002064
Authority: WO
Inventors: 박순현; 김정록; 김정기; 이민정
Original assignee: (주)경인양행
Priority date: 2012-05-23
Filing date: 2013-03-14
Publication date: 2013-11-28
Also published as: KR101380942B1; KR20130130976A

Abstract

The present invention relates to a triarylmethane blue dye compound for a color filter, wherein a blue resin composition including same has the characteristics of good dissolvability of organic solvents such as propylene glycol methyl ether acetate (PGMEA), good mixability with other dyes, and high luminance, and high heat resistance, and a color filter using same can be manufactured so as to have good heat resistance and luminance.

Description

Triarylmethane blue dye compound, blue resin composition for the color filter comprising the same 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.

The liquid crystal display displays an image by using optical and electrical properties of the liquid crystal material. The liquid crystal display device has advantages such as light weight, low power, low driving voltage, and the like compared to a CRT, a plasma display panel, and the like. The liquid crystal display device includes a liquid crystal layer positioned between glass substrates. Light generated from the light source passes through the liquid crystal layer, and the liquid crystal layer controls light transmittance. The light passing through the liquid crystal passes through the color filter layer and implements a full color screen by additive mixing using light passing through the color filter layer.

In general, dyeing, printing, electrodeposition, and pigment dispersing methods are known as color filter manufacturing methods for liquid crystal display devices. In the past, methods of using dyes have been studied. However, when dyes are used, heat resistance, light resistance, It is difficult to apply because of low chemical resistance, etc., compared to pigments, and the pigment dispersion method is generally applied at present because there is no economical efficiency due to a complicated process in the dyeing method. Pigments are less transparent than dyes but have been overcome by advances in pigment miniaturization and dispersion techniques. Since the color filter manufactured by the pigment dispersion method uses pigments, it is stable against light, heat, solvents, etc., and when patterned by photolithography, it is easy to manufacture color filters for large screens and high-precision color displays. 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 the method of producing a color filter by the pigment dispersion method, a color resist solution is first applied onto a substrate by a spin coater and dried to form a coating film. Subsequently, a color pixel is obtained by pattern exposure and development of a coating film, it heat-processes at high temperature, the pattern of a 1st color is obtained, and this operation is repeated according to the number of colors, and a color filter is produced. The most important factors influencing the performance of the color resist are the properties of the pigment used as the colorant, its dispersibility, and the dispersion state. Recently, with the increase in size and high definition of LCDs, the demand characteristics of color filters such as high transmittance of color layer, high contrast ratio, narrow black matrix width and high reliability are increasing every year. As a means for satisfying these requirements, color pigments such as brightness and contrast ratio have been satisfied by miniaturizing the pigment as far 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 difficult storage and transportation conditions in order to maintain optimum quality.

In the case of the pigment dispersion, the pigment is present in the form of particles, which not only scatters the light but also causes the pigment surface area to increase rapidly due to the miniaturization of the pigment, thereby producing color resists due to the generation of uneven pigment particles due to deterioration of dispersion stability. There is a difficulty.

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

As an alternative, studies have been conducted to improve the brightness and contrast ratio by using a hybrid type of coloring agent which improves physical properties by mixing pigments and dyes. Through this, a certain level of brightness and contrast ratio has been improved. Since some dye is added to the material, the effect of improving physical properties is not so great.

In order to solve this problem and to achieve high brightness, high contrast ratio and high resolution, it has recently been considered to use a dye instead of a pigment as a colorant. Many attempts have been made using triarylmethane dyes as blue colorants. In general, triaryl methane dye has a high transmittance at 420-450 nm of the color filter, but the solubility of the solvent used in the color composition for the color filter is inferior, and heat resistance is poor. In general, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and the like are commonly used as the solvent used in the coloring composition for color filters. In the case of solubility in cyclohexanone is easy to secure, but solubility in PGMEA or PGME has a low problem. However, cyclohexanone is prohibited from being used as an environmentally harmful substance, which requires a dye having high solubility in PGMEA or PGME.

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

As another example, a study of compounds of triarylmethane cations and anions of other dyes has been conducted, but these compounds have some heat resistance, but still have poor solubility in ester organic solvents such as PGMEA.

Therefore, the problem to be solved by the present invention is to solve the above problems, to ensure the brightness and contrast ratio, etc. superior to the pigment and to solve the problems such as heat resistance of the existing 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 same.

The present invention to solve the above problems,

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

[Formula 1]

In [Formula 1],

X ^- is trifluoromethanesulfonic acid or bistrifluorotansulfonimide anion,

R ₁ , R ₂ , R ₃ and R ₄ are each 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 represented by the following [formula 1]: Is any one selected from R ₅ ,

At least one of R ₁ , R ₂ , R _3, and R ₄ includes R ₅ ,

N is an integer of 1 to 10,

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

In [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.

[Formula 2]

In [Formula 2],

X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,

R ₇ , R ₈ , R ₉ and R ₁₀ are each 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 as [Formula 2] Is any one selected from R ₁₁ displayed,

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

N is an integer of 1 to 10,

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

[Formula 2]

In [Formula 2],

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

In addition, the present invention to solve the above problems,

Blue dye compounds; Binder resins; Reactive unsaturated compounds; Polymerization initiator; Organic solvents; 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 include a blue pigment as necessary, and the blue pigment may be a copper phthalocyanine-based blue pigment.

According to another embodiment of the present invention, the reactive unsaturated compound is a thermosetting monomer or oligomer; Photocurable monomers and oligomers; And it may be selected from the group consisting of 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.

In addition, the present invention 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 in a hot plate at 90 ℃ and at room temperature Cool for 1 minute. After exposing this to an exposure dose (365 nm standard) of 100 mJ / cm 2 using an exposure machine, postbake is performed at 220 ° C. for 30 minutes, and then is a transmittance graph (UV-vis-spectrum) according to wavelength. .

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].

[Formula 1]

In [Formula 1],

X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,

At least one of R ₁ , R ₂ , R _3, and R ₄ includes R ₅ ,

N is an integer of 1 to 10,

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

In [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].

[Formula 2]

In [Formula 2],

X ^- is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,

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

N is an integer of 1 to 10,

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

[Formula 2]

In [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 used by selecting one or more of the blue pigments generally used in the conventional colored resin composition for color filters, and may include a copper phthalocyanine-based blue pigment. Examples of the copper phthalocyanine-based blue pigments include compounds classified as pigments in the Color Index (Published by The Society of Dyers and Colourists). 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 luminance by having excellent transmittance at 420 nm to 450 nm by using the compound dye of [Formula 1] or [Formula 2] according to the present invention.

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

For example, cellulose resins, in particular carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose, acrylic acid resins, alkyd resins, melamine resins, epoxy resins, polyvinyl alcohols, polyvinyl pyrrolidones, polyamides, polyamide-imines, Binders, such as polyimide, are useful.

Useful binders also include resins having photopolymerizable unsaturated bonds, for example acrylic resins. 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, male Copolymers between anhydrides, polymerizable monomers containing carboxylic groups such as monoalkyl maleates, and polymerizable monomers such as methacrylic acid, styrene and styrene derivatives are useful.

Examples include compounds containing an oxirane ring and an ethylenically unsaturated compound, for example, glycidyl (meth) acrylate, acryloyl glycidyl ether and monoalkylglycidyl itaconate and the like carboxyl- Reaction products of the containing polymerized compounds, and compounds containing hydroxyl groups and ethylenically unsaturated compounds (unsaturated alcohols), respectively (e.g. allyl alcohol, 2-butene-4-ol, oleyl alcohol, 2-hydroxyethyl There are reaction products of (meth) acrylate, N-methylolacrylamide and the like and a carboxyl-containing polymerized compound, and such a binder may contain an unsaturated compound having no isocyanate group.

The equivalent amount of unsaturation of the binder (molecular weight of binder per unsaturated compound) is generally in the range of 200 to 3,000, in particular in the range of 230 to 1,000, in order to provide not only suitable photopolymerization but also 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, particularly 10,000 to 50,000 g / mol.

The reactive unsaturated compound may be selected from the group consisting of a thermosetting monomer or oligomer, a photocurable monomer or oligomer, and a combination thereof, preferably the photocurable monomer, at least one reactive double bond and further reactive in the molecule May contain groups.

Useful photocurable monomers in this connection are in particular reactive solvents or reactive diluents, for example mono-, di-, tri- and polyfunctional 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 purpose. As a preferred example, fatty acids, fatty amines, alcohols, bean oils, waxes, rosins, resins, benzotriazole derivatives, and the like may be used to improve surface texture. More preferably, as the fatty acid, Stearic acid or Behenic acid may be used, and as the fatty amine, Stearylamine may be used.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those who have knowledge.

Synthesis Example 1. Synthesis of Compound Represented by Formula 3

(1) Synthesis of Compound

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

Scheme 1

[Formula 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].

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].

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 replace 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].

Scheme 4

[Formula II] [Formula 4]

After dissolving 100 mL of methanol in 10.00 g (13.58 mmol), 4.29 g (14.94 mmol) of lithium bistrifluoromethanesulfonimide 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].

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 the reaction was completed, water was added, the layers were separated, 20 mL of saturated sodium chloride solution was added thereto, followed by stirring, followed by stirring 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].

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].

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].

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 bistrifluoromethanesulfonimide 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].

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].

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 that the 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

The photosensitive blue resin composition was manufactured with the following composition.

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

(b) Acrylic monomer: dipentaerythritol hexaacrylate 10 g

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

(d) Photoinitiator: 2 g Irgaeure OXE-01 from 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 a 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 the compound of Synthesis Example 3 was used as a blue dye compound.

Example 4 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 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 C.I. Blue pigment 15: 6 1.65 g, C.I. Purple pigment 23 was prepared using 0.65 g.

Comparative Example 2

A photosensitive blue resin composition was prepared in the same manner as in Example 1, but prepared by adding 2.3 g of the compound of [Compound] of the comparative example instead of the blue dye compound.

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

In order to measure the brightness and contrast ratio, a blue resin composition for color filters prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was spin-coated to a thickness of 2 μm on a glass substrate of 10 cm × 10 cm, respectively, at a temperature of 90 ° C. 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.

Subsequently, after performing a postbake for 30 minutes in a convection oven at 220 ° C., luminance was measured using a spectrophotometer MCPD3700 of Otsuka electronic, and using CT-1 of Tsubosaka Co., Ltd. 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].

TABLE 2

division	x	y	Luminance	Contrast Ratio
Example 1	0.1457	0.113	14.63	14274
Example 2	0.1463	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 pigments, and particularly, in Example 4, 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 Comparative Example 2, the luminance was lowest because of the low transmittance at 420-450 nm, and in Examples 1 to 4, the luminance 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

For heat resistance measurement, the blue resin compositions for color filters prepared in Examples and Comparative Examples were spin-coated to a thickness of 2 μm on a 10 cm × 10 cm glass substrate, respectively, and prebaked for 3 minutes on a 90 ° C. hot plate. -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.

After 30 minutes postbake in a convection oven at 220 ° C., the color characteristics were checked using a spectrophotometer MCPD3700 of Otsuka electronic, and further 1 hour in a 220 ° C. convection oven. After the heat treatment was performed, the color characteristics were again determined, and ΔEab * values were obtained.

TABLE 3

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

In general, it is known to satisfy the reliability only when ΔEab * 3 or less is satisfied.

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.

Since the triarylmethane blue dye compound according to the present invention has excellent solubility, high heat resistance, and high brightness in propylene glycol monomethyl ether acetate (PGMEA), it is possible to produce a color filter having higher brightness and higher contrast ratio than a color filter using a conventional pigment. It is possible.

Claims

Triarylmethane blue dye compound represented by the following [Formula 1]:

[Formula 1]

In [Formula 1],

X - is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,

R 1 , R 2 , R 3 and R 4 are each 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 represented by the following [formula 1]: Is any one selected from R 5 ,

At least one of R 1 , R 2 , R 3, and R 4 includes R 5 ,

N is an integer of 1 to 10,

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

In [Formula 1],

M is an integer of 1 to 10, and R 6 is hydrogen or methyl.
Triarylmethane blue dye compound represented by the following [Formula 2]:

[Formula 2]

In [Formula 2],

X - is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,

R 7 , R 8 , R 9 and R 10 are each 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 as [Formula 2] Is any one selected from R 11 displayed,

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

N is an integer of 1 to 10,

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

[Formula 2]

In [Formula 2],

M is an integer of 0 to 10, and R 12 is hydrogen or methyl.
The method of claim 1,

[Formula 1] is a triarylmethane blue dye compound, characterized in that the compound represented by the following [Formula 3] or [Formula 4]:

[Formula 3]

[Formula 4]
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]:

[Formula 5]

[Formula 6]
Blue dye compounds; Binder resins; Reactive unsaturated compounds; Polymerization initiator; Organic solvents; And additives;

The blue dye compound is a blue dye compound represented by the above [Formula 1] according to claim 1; Or a blue dye compound represented by the above [Formula 2] according to claim 2; Blue resin composition for a color filter, characterized in that.
The method of claim 5,

The blue dye compound is a blue resin composition for a color filter, characterized in that it further comprises one or more selected from xanthene dyes, cyanine dyes and azapopyrine dyes.
The method of claim 5,

The blue dye compound is a blue resin composition for a color filter, characterized in that 0.01 to 50% by weight relative to the total weight of the blue resin composition.
The method of claim 5,

The blue resin composition may further include a blue pigment, and the blue pigment is a blue phthalocyanine-based blue pigment, wherein the blue resin composition for a color filter.
The method of claim 5,

The reactive unsaturated compound may be a thermosetting monomer or oligomer; Photocurable monomers and oligomers; And a blue resin composition for color filters, characterized in that selected from the group consisting of these.
The method of claim 5,

The polymerization initiator is a blue resin composition for a color filter, characterized in that 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 Claim 5.