KR101661733B1 - Dye compounds and resin composition for color filter comprising the same - Google Patents

Abstract

The present invention relates to a dye compound for a color filter, characterized in that it is a dye compound according to the following formula (1), and the resin composition comprising the dye compound according to the present invention is an organic compound such as propylene glycol methyl ether acetate Excellent solubility in solvents, high heat resistance, and particularly excellent light resistance, and it is possible to manufacture excellent color filters by using them.
[Chemical Formula 1]

Description

DYE COMPOUNDS AND RESIN COMPOSITION FOR THE COLOR FILTER CONTAINING THE SAME

More particularly, the present invention relates to a triarylmethane dye compound having high solubility in an organic solvent and excellent heat resistance and light fastness, and a resin composition for a color filter using the dye compound. .

Dye compounds have been applied to various fields due to their color absorption or transmission properties. In particular, it is widely used in the fields of textile industry used as a fiber coloring agent, display materials, inkjet ink composition, writing instrument coloring agent, and especially in biochemistry used for dyeing cells and tissues.

Among these dye compounds, the Victoria Blue BO compound, which is a widely used triarylmethane compound and is widely used, has excellent color characteristics, but has poor solubility and heat resistance to an organic solvent and is not particularly excellent in light resistance. , Inkjet ink, and writing instrument coloring agent.

[Victoria Blue BO]

In general, the light-induced decomposition mechanism of triarylmethane-based dyes is well described in the following reference (Dyes and Pigments 3 (1982) 49-58).

In order to improve the above-mentioned limitation of the above-mentioned Victoria Blue BO compound, various attempts have been made to improve the physical properties by replacing the anion of Victoria Blue BO by an alkylsulfonic acid anion, an aromatic sulfonic acid anion, oxalate, an alkylcarboxylic acid anion or the like . Although many improvements in solubility and heat resistance have been made with such a salt solution, the improvement in light resistance has not been largely improved.

Accordingly, it is an object of the present invention to provide a novel triarylmethane dye capable of improving solubility in an organic solvent and having excellent heat resistance, Compound. ≪ / RTI >

The present invention also provides a resin composition for a color filter comprising the novel triarylmethane dye compound as a colorant and a color filter using the same.

In order to solve the above problems, the present invention provides a triarylmethane dye compound represented by the following formula (1).

[Chemical Formula 1]

The specific structure and substituent of the above formula (1) will be described later.

The present invention also provides a resin composition for a color filter comprising a colorant, a reactive unsaturated compound, a polymerization initiator, an organic solvent and an additive, wherein the colorant comprises a dye compound according to the above formula (1) The present invention also provides a resin composition for a color filter.

In addition, the colorant may further include at least one selected from the group consisting of a dye and a pigment in consideration of the color coordinate and color correction of the color filter.

In addition, the colorant may be 0.01% by weight to 50% by weight based on the total weight of the resin composition.

The reactive unsaturated compound may be at least one selected from the group consisting of thermosetting monomers and oligomers, photocurable monomers and oligomers, and combinations thereof.

The polymerization initiator may be any one selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, and a combination thereof.

The dye compound according to the present invention has excellent solubility, heat resistance and light resistance to propylene glycol monomethyl ether acetate (PGMEA). Therefore, when it is used as a coloring agent for a color filter resin composition, the solubility is higher than that of a pigment, and the amount of additives to be added for stabilizing the dispersion of pigments can be reduced, thereby having an advantage of maximizing coloring power. This has the advantage.

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

In order to apply a dye as a coloring agent to a color filter, excellent solubility in an organic solvent, high heat resistance and high light resistance are required. Recently, dyes having high transmittance have been developed as coloring agents for color filters. However, dyes satisfying excellent solubility, high heat resistance and high light resistance to organic solvents are rarely present.

The inventors of the present invention have conducted various experiments and have synthesized triarylmethane dyes excellent in solubility, heat resistance and light resistance, and confirmed that the triarylmethane dyes can be applied as coloring agents for color filter resin compositions.

The dye compound according to the present invention is characterized by being a dye compound represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1)

X ^- may be a fluorinated alkylsulfonic acid anion or a bistrifluoromethanesulfonimide anion.

R ₁ , R ₂ , R ₈ And R < ₉ > are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group selected from the following Structural Formulas 1 and 2, wherein R ₁ , R ₂ , R ₈ And R ₉ Is at least one of [structural formula 1] or [structural formula 2].

[Structural formula 1] [Structural formula 2]

In the above Structural Formulas 1 to 2,

R ₁₀ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R ₁₁ is hydrogen or methyl, R ₁₂ And R < ₁₃ > are the same or different and each independently represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.

R ₃ , R ₄ , R ₅ , R ₆ And R ₇ are the same or different from each other and each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, A cycloalkoxy group having 3 to 10 ring carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, and halogen.

a, b, c is an integer from 0 to 4, respectively, d, e is an integer from 0 to 5, wherein a, b, c, d, and when e is 2 or more, a plurality of R _3, R _4, R ₅ , R ₆ And R < ₇ > may be the same or different from each other.

The above R _{1 ,} R _{2 ,} R ₈ And R ₉ is more specifically a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms which is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Butyl group, an i-pentyl group, a t-butyl group, a 2-ethylhexyl group, and an alkyl group additionally substituted thereto. As the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a cycloalkyl group And so on. Examples of the substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms may include a benzyl group, a naphthylalkyl group, and an aralkyl group additionally substituted thereon. The substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms may be a phenyl group, a naphthyl group, and an aromatic hydrocarbon group additionally substituted thereto.

In the above structural formula 1, R ₁₀ may more specifically be a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an alkylene group additionally substituted thereto, or the like.

In the above formula 2, R ₁₂ And R ₁₃ may each be a methylene group, an ethylene group, a propylene group, a butylene group, and an alkylene group additionally substituted thereto.

R ₃ , R ₄ , R ₅ , R ₆ And R ₇ are more specifically a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms which may have a substituent selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, , an i-butyl group, an i-pentyl group, a t-butyl group, a 2-ethylhexyl group and an alkyl group additionally substituted thereto. As the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a cycloalkyl group And so on. Examples of the substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, nonyloxy, decyloxy, i- -Butoxy, i-pentoxy, t-butoxy, 2-ethylhexyloxy and also alkoxy groups additionally substituted on these groups. Further, examples of the substituted or unsubstituted cycloalkoxy group having 3 to 10 carbon atoms include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, And the like.

The dye compound according to Formula 1 of the present invention can be specifically represented by the following [1] to [16], but the scope of Formula 1 according to the present invention is not limited thereto.

The resin composition for a color filter according to the present invention may contain a binder resin, a reactive unsaturated compound, a polymerization initiator, an organic solvent and an additive, using a dye compound represented by the formula (1) according to the present invention as a colorant.

The colorant may further include at least one dye compound or pigment compound together with the dye compound of formula (I) according to the present invention in consideration of the color coordinate and color correction of the color filter.

Examples of the dye compounds include xanthene dyes, cyanine dyes, and azapphyrin dyes. The pigment compounds may be blue pigments or purple pigments, and may be used without any particular limitation. of Dyers and Colourists). < / RTI > Specific examples include C.I. 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60 and the like can be mentioned as color pigments (Color Index Pigment Blue). And Color Index Pigment Violet 23 and the like.

The colorant may be contained in an amount of 0.01 to 50% by weight based on the total weight of the resin composition for a color filter.

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

For example, cellulose resins such as carboxymethylhydroxyethylcellulose and hydroxyethylcellulose, acrylic acid resin, alkyd resin, melamine resin, epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, polyamide, polyamide- Polyimide and the like. More preferably, a resin having a photopolymerizable unsaturated bond is included, and for example, it may be an 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, A copolymer of a polymerizable monomer containing a carboxyl group such as an anhydride and a monoalkyl maleate and a polymerizable monomer such as a methacrylic acid, a styrene and a styrene derivative is useful, and a compound containing an oxirane ring and an ethylenically unsaturated compound , For example, a reaction product of a carboxyl-containing polymer compound with glycidyl (meth) acrylate, acryloyl glycidyl ether, monoalkyl glycidyl itaconate, etc., and a reaction product of a hydroxyl group and an ethylenically unsaturated compound (Unsaturated alcohols), for example, allyl alcohol, 2-buten-4-ol, oleyl Alcohol, 2-hydroxyethyl (meth) acrylate, N- methylol acrylamide as the carboxyl group-containing, and the reaction product of a polymerizable compound, the binder may also contain an unsaturated compound with 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. In order to provide sufficient alkali developability after film exposure, the acid number may generally be from 20 to 300, in particular from 40 to 200. 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 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 type are known in the art and are described, for example, in Roempp, Lexikon, Lacke und Druckfarben, et al. Ulrich Zorll, Thimem Verlag Stuttgart-New York, 1998, p 491/492. The choice of monomers will depend, inter alia, on the type and intensity of the irradiation used, the desired reaction by the photoinitiator and the film properties. These photocurable monomers may be used alone or in combination of monomers.

The polymerization initiator may be a thermosetting initiator, a photo-curing initiator, or a combination thereof, and may preferably be a photo-curing initiator. Such a photo-curing initiator may be, for example, the result of absorption of visible light or ultraviolet light, To form a reaction intermediate capable of inducing polymerization of the binder. Photoinitiators or are known in the art, see for example Roempp, Lexikon, Lacke und Druckfarben, et al. 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. Examples of the ketone group include acetone, methyl ethyl ketone, and cyclohexanone, and the alkylene glycol ether group includes methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methylol solos 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 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 Methyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol and the like may be used. Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, Examples of the aromatic solvent group 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.

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, stearic acid or behenic acid may be used as the fatty acid, and stearylamine may be used as the fatty amine.

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>

1. Synthesis of Synthetic Example

(1) Synthesis of Compound of Formula (I)

A compound represented by the formula (I) was synthesized according to the following Reaction Scheme 1.

[Reaction Scheme 1]

[Chemical Formula a] [Chemical Formula h] [Chemical Formula I]

80.00 mmol of [Formula a] was added with 320 mL of Toluene and stirred. Then, 480.00 mmol of phosphorus oxychloride was added and stirred for 15 minutes. 80 mmol of [Formula h] was added, and the mixture was refluxed. After completion of the reaction, cooling at room temperature was continued, 300 mL of water was added, and the mixture was stirred. After layer separation, concentration under reduced pressure was carried out, and the obtained compound was purified by column chromatography to obtain 55.71 mmol of the compound of the formula (I), and the molecular weight was confirmed by LC / MS.

(2) Synthesis of compounds of the formulas (II) to (VIII)

Benzophenone derivatives and aniline derivatives were selected as shown in the following Table 1 and the synthesis was carried out in the same manner as in the synthesis of the compound of the formula (I) by selecting reactants as shown in the following [Table 2] ]. The synthesized [Formula II] to [Formula VIII] were confirmed by LC / MS.

[Table 1]

[Table 2]

(3) Synthesis of Synthesis Example 1

[Synthesis Example 1]

20.00 mmol of the compound of formula (I) was dissolved in 100 g of dichloromethane and dissolved with stirring. 24.00 mmol of sodium trifluoromethanesulfonate was added thereto as a 20% aqueous solution and stirred for 1 hour to replace the salt. After layer separation, the organic layer was washed with water, concentrated under reduced pressure, and purified to obtain 14.68 mmol of the compound of Synthesis Example 1.

(4) Synthesis of Synthesis Examples 2 to 16

Synthesis was carried out in the same manner as in Synthesis Example 1 except that the reaction product was selected from the compounds represented by the formulas (I) to (VIII) as shown in the following Table 3 and sodium trifluoromethanesulfonate (A) or lithium bistrifluoride (B), and lithium nonafluorosulfonate (C) were synthesized.

[Table 3]

(5) Synthesis of Comparative Examples 2 to 3

Synthesis was carried out in the same manner as in Synthesis Example 1. Except that Victoria Blue BO (Comparative Example 1) was selected as the following reactant, and the sodium trifluoromethanesulfonate (A) was selected as the salt compound, and the compound of Comparative Example 2 was also synthesized. Lithium bistrifluoromethane sulfonimide B) was selected to synthesize Comparative Example 3.

[Comparative Example 1] [Comparative Example 2] [Comparative Example 3]

2. Solubility assessment

Synthesis Examples 1 to 16 and Comparative Examples 1 to 3 were dissolved in PGMEA to confirm their respective solubilities, and the results are shown in Table 4 below.

[Table 4]

As a result of Synthesis Examples 1 to 16 and Comparative Examples 1 to 3 in Table 4, it was confirmed that the solubility showed a large difference depending on the anion. In the case of Comparative Example 1 in which the salt was not substituted, it was found that the solubility was as low as <1%, and the solubility was increased in the order of chloride, fluorinated alkylsulfonic acid anion and bistrifluoromethanesulfonimide anion . In particular, in the case of the bistrifluoromethanesulfonimide anion, the solubility is excellent, i.e., > 10%.

3. Preparation of Resin Composition

For the evaluation of heat resistance and light resistance, the resin compositions of Examples 1 to 16 and Comparative Examples 4 to 6 were prepared as follows.

(1) Example 1 Production of resin composition

A resin composition was prepared in the following composition.

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

(b) Acrylic monomer: 10 g of dipentaerythritol hexaacrylate

(c) Dye compound: Synthesis Example 1 2.3 g

(d) Photopolymerization initiator: 2 g of Irgacure OXE-02 manufactured by BASF

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

(2) Examples 2 to 16 and Comparative Examples 4 to 6 Preparation of resin composition

A resin composition was prepared in the same manner as in Example 1 except that the dye compound was changed to the compound shown in Table 5 instead of the compound of Synthesis Example 1 to prepare a resin composition.

[Table 5]

4. Property evaluation

(1) Heat resistance measurement

For the measurement of the heat resistance, the resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on a glass substrate of 10 cm x 10 cm in thickness of 2 mu m and pre-baked on a hot plate at 90 DEG C for 3 minutes And then cooled at room temperature for 1 minute. This was exposed using an exposure machine at an exposure amount of 100 mJ / cm 2 (based on 365 nm).

After post-baking for 20 minutes in a convection oven at 230 ° C, the color characteristics were confirmed using a spectrophotometer, MCPD3700 from Otsuka electronic Co., Ltd., and an additional one hour at 230 ° C in a convection oven After the heat treatment, the color characteristic was confirmed again and the value of [Delta] Eab * was obtained, and it is shown in Table 6 below.

(2) Light resistance measurement

After the spin coating, exposure and post-baking were carried out in the same manner as in the heat resistance measurement, the color characteristics were confirmed using a spectrophotometer, MCPD3700 manufactured by Otsuka electronic Co., Ltd., and 1.34 W / m 2 / ) For 8 hours, and the color characteristic was confirmed again, and the value of [Delta] Eab * was obtained, and the results are shown in Table 6 below.

[Table 6]

In Table 6, it can be seen that the heat resistance is improved in the order of chloride, fluorinated alkylsulfonic acid, and bistrifluoromethanesulfonimide in Comparative Examples 4 to 6, and in Examples 1 to 16 and Comparative Examples 4 to 6, 6 shows that the heat resistance and the light resistance of the examples are superior to those of the comparative examples.

Claims (9)

A dye compound represented by the following Chemical Formula 1:
[Chemical Formula 1]

In the above formula (1)
X ^- is a fluorinated alkylsulfonic acid anion or a bistrifluoromethanesulfonimide anion,
R ₁ , R ₂ , R ₈ and R ₉ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, 7 to 20 aralkyl groups, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 10 carbon atoms, and [Structural Formula 1]
[Structural formula 1]

In the above formula 1,
R ₁₀ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R &lt; ₁₁ &gt; is methyl,
R ₈ and R ₉ are different from each other, and any one of R ₈ and R ₉ is the above-mentioned [formula 1]
R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, An alkoxy group having 1 to 10 ring carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms and halogen,
a, b and c are integers of 0 to 4, d and e are integers of 0 to 5, and when a, b, c, d and e are 2 or more, a plurality of R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are the same or different from each other. The method according to claim 1,
The dye compound represented by Formula 1 is selected from the compounds represented by the following [1] to [6], [9] to 12], [15]

coloring agent; Binder resin; Reactive unsaturated compounds; A polymerization initiator; Organic solvent; And an additive,
The resin composition for a color filter according to claim 1, wherein the coloring agent comprises the dye compound according to claim 1. The method of claim 3,
Wherein the colorant further comprises at least one dye selected from xanthene dyes, cyanine dyes and azapphyrin dyes. The method of claim 3,
Wherein the resin composition further comprises a blue pigment or a violet pigment. The method of claim 3,
Wherein the colorant is 0.01% by weight to 50% by weight based on the total weight of the resin composition. The method of claim 3,
Wherein the reactive unsaturated compound is at least one selected from the group consisting of thermosetting monomers and oligomers, photocurable monomers and oligomers, and combinations thereof. The method of claim 3,
Wherein the polymerization initiator is at least one selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, and a combination thereof. A color filter using the dye compound according to claim 1 or a dye compound synthesized using the dye compound as a colorant.