KR20150092918A - Polymer dye compounds, resin composition comprising the same for color filter and color filter using the same - Google Patents

Abstract

The present invention relates to a dye polymer compound used as a coloring resin composition for a color filter, which is represented by [Chemical formula 1] or [Chemical formula 2]. According to the present invention, the dye polymer compound has excellent thermal resistance and chemical resistance, and, especially, improved light resistance. Thus, the dye polymer compound of the present invention can be applicable to various dye materials using the same, and especially to a resin composition for a color filter, which is a display material.

Description

[0001] The present invention relates to a dye polymer compound, a resin composition for a color filter containing the same, and a color filter using the polymer composition.

The present invention relates to a dye polymer compound, a resin composition for a color filter comprising the same, and a color filter using the same. More specifically, the present invention relates to a triarylmethane dye polymer compound having excellent heat resistance and chemical resistance, particularly light resistance.

In general, dyes have higher luminance and higher solubility in organic solvents than pigments. Therefore, attempts have been made to apply dyes to displays, but due to problems such as heat resistance, chemical resistance and light resistance, development of color filters using pigments as colorants has been under way for some time. However, in order to fabricate a color filter using a pigment, it is necessary to refine the particles in order to increase the luminance.

In the pigment refining process, the pigments should be finely processed to a size of several tens of nanometers or less by proceeding with a process such as salt milling. As the pigment particles become finer, the luminance becomes higher. On the contrary, it becomes more difficult to secure the dispersion stability of the finely dispersed pigment particles, and various additives are needed for securing stability.

In recent years, color filters using pigments have become more difficult to manufacture due to increased demands for high-brightness color filters. Studies using dyes having improved chemical resistance, heat resistance, and light resistance have been underway as alternatives. For example, Attempts have also been made to prepare a colored resin composition and a color filter using a triarylmethane dye having a high molecular weight.

Although many improvements have been made in heat resistance by using anion substitution of triarylmethane dyes, they have been limitedly used in color filters because of their lower solubility than pigments and lower resistance to chemicals and lower light resistance than pigments.

Korean Patent Publication No. 10-2013-0130976

In order to solve the above problems, the present invention provides a triarylmethane dye polymer having high solubility with a solvent and excellent heat resistance, chemical resistance, and particularly light resistance.

The present invention also provides a colored resin composition capable of producing a color filter having high brightness using the triarylmethane dye polymer.

The inventors of the present invention have studied the substituents of the triarylmethane dyes in order to solve the above problems and found that the light resistance is improved when aromatic hydrocarbonsubstituents or benzyl substituents are present as a result of checking the properties of the triarylmethane dyes in different substituents Respectively.

Accordingly, the present invention provides a triarylmethane polymer dye compound applicable as a coloring agent for a color filter.

More specifically, the present invention provides a homopolymer compound containing only a triarylmethane dye compound structure represented by the following formula (1) or (2).

And further includes at least one compound structure represented by a compound structure represented by the following formulas (3) to (6), which comprises at least one triarylmethane dye compound structure represented by the following formulas (1) to Based on the total weight of the copolymer.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

According to one embodiment of the present invention, the monomer compound corresponding to the structure represented by Formula 1 is a compound represented by Formula 7, and the monomer compound corresponding to the structure represented by Formula 2 is represented by [ Is a compound represented by the formula (8).

(7)

[Chemical Formula 8]

According to one embodiment of the present invention, the monomer compounds corresponding to the structures represented by the above formulas (3) to (6) are the compounds represented by the following formulas (9) to (12), respectively.

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The structures and substituents of the above formulas (1) to (12) will be described later.

The present invention also provides a resin composition for a color filter comprising a dye compound, a binder resin, a reactive unsaturated compound, a polymerization initiator, an organic solvent and an additive as a colorant, wherein the dye compound is a dye polymer compound according to the present invention .

The dye polymeric compound according to the present invention exhibits higher luminance than the conventional pigment using triarylmethane polymer compounds having excellent luminance as a coloring agent and has improved chemical resistance compared with the case of using a dye monomer compound, It is possible to manufacture a color filter having a high luminance by using a colored resin composition using the same to improve the weak light resistance of a dye.

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

One aspect of the present invention relates to a dye polymer compound suitable for a resin composition for a color filter, and is characterized by excellent heat resistance, chemical resistance, light resistance, and the like.

The dye polymer compound according to the present invention is a compound necessarily containing the structure represented by the following formula (1) or (2), and is a polymer compound containing only the dye compound structure represented by formula (1) , And further comprises any one or more structures selected from the structures of the dye compounds of the following formulas (1) to (2), and further comprising at least one selected from the structures of the compounds represented by formulas (3) to May be a polymer compound.

[Chemical Formula 1]

In the above formula (1)

X ^- is a bis (trifluoromethane) sulfonimide anion, nonafluorobutanesulfonic acid anion or tetrakis (pentafluorophenyl) borate anion.

R ₅ , R ₆ and Y each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a halogen group.

At least two or more of R ₁ , R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted aromatic hydrocarbon or a substituted or unsubstituted benzyl group having 6 to 10 carbon atoms, Or an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, an allyl group, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, or a substituted or unsubstituted benzyl group.

R ₇ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, n is 0 or 1, and R ₈ is hydrogen or methyl.

(2)

In the above formula (2)

X ^- is a bis (trifluoromethane) sulfonimide anion, nonafluorobutanesulfonic acid anion or tetrakis (pentafluorophenyl) borate anion.

R ₁₃ , R ₁₄ and Y each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a halogen group.

R ₉ and R ₁₀ are each independently a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms or a substituted or unsubstituted benzyl group.

R _{11 and} R ₁₂ are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and R _{15 and} R ₁₆ are each independently hydrogen or methyl.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above Chemical Formulas 3 to 6,

R ₁₇ is selected from hydrogen, substituted or unsubstituted C 1 alkyl group of 1 to 18, substituted or non-substituted with an aromatic hydrocarbon and an epoxy or oxetane substituent of the ring having 6 to 10 carbon atoms, the substituent having a carbon number of 1 to 18, R ₁₈ is Hydrogen or methyl, and R ₁₉ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms.

The monomer constituting the polymer compound and corresponding to the structure represented by the formula (1) is a dye compound represented by the following formula (7).

(7)

In the above formula (7)

X ^- , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Y are the same as defined in the formula 1 and R ₂₀ is represented by the following formula 1.

[Structural formula 1]

In the above structural formula 1, n, R ₇ and R ₈ are the same as defined in the above formula (1)

The compound represented by the formula (7) may be a dye compound represented by the following structure, but is not limited thereto.

Among the dye compounds a-1 to a-24, R is pentafluorophenyl.

The monomer corresponding to the structure represented by the formula (2) is a dye compound represented by the following formula (8).

[Chemical Formula 8]

In the above formula (8)

X ^- , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and Y are the same as defined in Formula 2.

The compound represented by the formula (8) may specifically be a dye compound represented by the following structure, but is not limited thereto.

R shown in the dye compounds of the above b-1 to b-24 is pentafluorophenyl.

The monomers corresponding to the structures represented by the above formulas (3) to (6) as the polymer compound are each represented by the following formulas (9) to (12).

[Chemical Formula 9]

In the above formula (9), R < ₁₇ > And R < ₁₈ > each have the same definition as in the formula (3).

The compound represented by the above formula (9) is preferably selected from acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, isobutyl acrylate, decyl acrylate, lauryl acrylate, Ethylhexyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydroperfuryl acrylate, ethylene glycol methyl ether acrylate, 2-ethoxyethyl Acrylate, cinnamyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, allyl methacrylate, vinyl methacrylate , 2- (diethylamino) ethyl methacrylate 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, cinnamyl methacrylate, glycidyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3 , 4-epoxycyclohexylmethyl methacrylate.

[Chemical formula 10]

In the above formula (10), R ₁₇ is the same as defined in the formula (9).

The compound represented by the above formula (10) is preferably a vinyl formate, a vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl hexanoate, a vinyl octanoate, a vinyl decanoate, Stearate, vinyl methacrylate, vinyl cinnamate, vinyl benzoate, vinyl chloroacetate, vinyltrifluoroacetate, vinyl crotonate and vinyl 2-ethylhexanoate.

(11)

In the above formula (11), R ₁₇ is the same as defined in the above formula (9).

The compound represented by the above formula (11) is preferably maleimide, N-methylmaleimide, N-ethylmaleimide, N-benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

[Chemical Formula 12]

In the above formula (12), R ₁₉ is the same as defined in the above formula (6).

The compound represented by the above formula (12) is preferably selected from the group consisting of propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, (Ethylene glycol) vinyl ether, vinyl glycidyl ether, styrene, 4-trifluoromethylstyrene, methyl 4-vinylbenzoate, a-methylstyrene, 3-nitrostyrene, Styrene, 2-chlorostyrene, 3-chlorostyrene, and 2,4,6-trimethylstyrene.

The dye polymer compound according to the present invention is obtained by polymerizing a homopolymer compound obtained by polymerizing a dye compound represented by the formula (7) or (8) and at least one dye compound selected from the following formulas (7) Wherein at least one of the monomers is selected from the group consisting of the following formulas (12) to (12).

The weight average molecular weight (Mw) of the dye polymer compound according to the present invention is preferably 2,000 to 150,000, more preferably 2,000 to 30,000.

When the weight average molecular weight of the dye polymer compound is less than 2,000, the chemical resistance is not preferable, and when the molecular weight of the polymer is more than 150,000, the solubility may be lowered.

Another aspect of the present invention relates to a resin composition for a color filter, which is characterized by using a triarylmethane dye polymer containing a structure represented by any one of the above formulas (1) to (2) as a colorant, Resins, reactive unsaturated compounds, polymerization initiators, organic solvents and additives.

In addition, the colorant may optionally include a dye compound or a pigment compound together with the triarylmethane dye polymer compound as described in the present invention.

Examples of the dye compounds include xanthene dyes, cyanine dyes, and azapphyrin dyes. The pigment compounds may be used without particular limitation as long as they correspond to the blue-based pigments. The blue pigments preferably include a color index &Quot; The Society of Dyers and Colourists, " (Color Index Pigment Blue) 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16 and 60. Examples of the purple pigments include Color Index Pigment Violet 23 Lt; / RTI >

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

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, it may be an acrylic acid resin having a photopolymerizable unsaturated bond. For example, acrylate derivatives such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate, styrene and styrene derivatives, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and monoalkyl maleate A homopolymer such as a polymerizable monomer containing a carboxyl group or a copolymer between polymerizable monomers is useful.

Further, it is also possible to use a compound containing an oxirane ring and an ethylenically unsaturated compound such as glycidyl (meth) acrylate, acryloylglycidyl ether, monoalkylglycidyl itaconate, etc., A reaction product of a compound and a compound containing a hydroxyl group and an ethylenically unsaturated compound (unsaturated alcohol), respectively, such as allyl alcohol, 2-buten-4-ol, oleyl alcohol, 2-hydroxyethyl 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. 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, 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, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Example

1. Synthesis of polymer dyes

[Compound b-1] to [Compound b-1] to [Compound b-1] as the dye compound represented by the above formula [7] 24], the polymerization reaction was carried out to synthesize a dye homopolymer.

Further, at least one dye compound selected from the above-mentioned [compounds a-1] to [a-24] and [b-1] to [b-24] is selected and, as the polymerizable monomer compound, To select at least one compound from among the compounds represented by Formula 12 to proceed a polymerization reaction to synthesize a dye-copolymerized polymer.

Herein, the compounds corresponding to formulas (9) to (12) are selected from the following c) to m). C) to m) in Table 1 also refer to these compounds.

c) 2-ethylhexyl methacrylate

d) 2-ethylhexyl acrylate

e) methyl methacrylate

f) Shinnamil methacrylate

g) glycidyl methacrylate

h) 3-methacryloyloxymethyl-3-ethyloxetane

i) 3,4-epoxycyclohexylmethyl methacrylate

j) Methacrylic acid

k) Vinyl acetate

l) N-Phenylmaleimide

m) Cyclohexyl vinyl ether

(1) Synthesis of Synthesis Example 1

5.64 g of [compound a-1], 0.36 g of AIBN (azobisisobutyronitrile: polymerization initiator) and 33.34 g of MEK were placed in a 50 mL flask, and the mixture was stirred and dissolved. After proceeding with nitrogen purge, the temperature was raised and refluxed for 14 hours. Cooled to room temperature, concentrated under reduced pressure, and vacuum-dried to obtain a triarylmethane dye polymer compound having a number average molecular weight of 3110, a weight average molecular weight of 8121, and a dispersion degree of 2.61.

(2) Synthesis of Synthesis Example 2

A triarylmethane dye compound was prepared in the same manner as in Synthesis Example 1, except that [Compound b-1] was used in place of [Compound a-1] used in Synthesis Example 1 and a number average molecular weight of 3409, Thereby obtaining a triarylmethane dye polymer compound having a molecular weight of 1.71.

(3) Synthesis of Synthesis Example 3

3.00 g of [Compound a-1], 0.90 g of 2-ethylhexyl methacrylate c), 0.60 g of methyl methacrylate e), 0.90 g of methacrylic acid j) and 0.24 g of N-phenylmaleimide 1) , 0.36 g of AIBN (azobisisobutylonitrile: polymerization initiator) and 33.34 g of MEK were placed, refluxed, and dissolved by stirring. After proceeding with nitrogen purge, the temperature was raised and refluxed for 14 hours. Cooled to room temperature, concentrated under reduced pressure, and vacuum-dried to obtain a triarylmethane dye polymer compound having a number average molecular weight of 8440, a weight average molecular weight of 18401 and a dispersion degree of 2.18.

(4) Synthesis of Synthesis Examples 4 to 28

Synthesis was carried out in the same manner as in Synthesis Example 3, except that the dye compound and the polymerizable monomer compound were used as shown in Table 1 below.

The amount of compound used in [Table 1] is shown in g, and the number average molecular weight, weight average molecular weight and dispersity according to each synthesis example are shown in [Table 2].

Synthetic example compound c d e f g h i j k l m 4 a-2 3.00 0.90 0.60 0.90 0.24 5 a-3 3.00 0.80 0.80 0.60 0.44 6 a-4 3.00 0.80 0.80 0.44 0.60 7 a-5 3.00 0.50 0.70 0.54 0.90 8 a-6 3.00 0.64 0.90 0.50 0.60 9 a-7 3.00 0.74 0.70 0.50 0.30 0.40 10 a-8 3.00 0.40 0.40 1.00 0.84 11 a-9 3.00 1.20 0.50 0.94 12 a-10 3.00 0.70 0.74 1.20 13 a-11 3.00 1.20 0.40 0.50 0.54 14 a-12 3.00 1.00 1.00 0.40 0.24 15 b-1 3.00 0.40 0.60 0.70 0.94 16 b-2 3.00 0.50 0.40 0.40 0.34 1.00 17 b-3 3.00 1.50 0.34 0.50 0.30 18 b-4 3.00 1.00 1.00 0.34 0.30 19 b-5 3.00 0.10 0.50 1.10 0.94 20 b-6 3.00 1.10 0.30 0.80 0.44 21 b-7 3.00 0.40 0.40 0.70 1.14 22 b-8 3.00 0.70 1.20 0.74 23 b-9 3.00 0.50 1.00 0.80 0.34 24 b-10 3.00 0.60 0.54 0.50 1.00 25 b-11 3.00 0.20 0.10 0.40 0.30 0.64 1.00 26 b-12 3.00 1.00 0.50 0.40 0.40 0.34 27 a-1
b-1 1.50
1.50 1.00 0.50 0.40 0.40 0.34 28 a-1
b-4 1.50
1.50 1.00 1.20 0.34

Synthetic example Number average molecular weight Weight average molecular weight Dispersion degree 4 8864 16842 1.90 5 8299 15520 1.87 6 8503 16240 1.91 7 9730 17514 1.80 8 10050 17889 1.78 9 10475 23150 2.21 10 8772 15264 1.74 11 8386 14089 1.68 12 9781 19465 1.99 13 10103 24753 2.45 14 7032 11321 1.61 15 8902 15134 1.70 16 7119 12956 1.82 17 6463 15577 2.41 18 6383 11744 1.84 19 6297 13980 2.22 20 6140 10623 1.73 21 6278 16009 2.55 22 6554 13304 2.03 23 6043 11845 1.96 24 5760 12097 2.10 25 4863 9871 2.03 26 6928 14410 2.08 27 6669 12938 1.94 28 6420 13162 2.05

2. Preparation of Resin Composition

(1) Example 1 Production of resin composition

A resin composition was prepared in the following composition.

, 1.4 g of a copolymer (Mw = 20,000) of benzyl methacrylate / methacrylic acid (weight ratio 60:40) as binder resin, 5.0 g of dipentaerythritol hexaacrylate as an acrylic monomer, 5.0 g of the dye polymer prepared according to Synthesis Example 1 1.9 g of the compound, 1.0 g of Irgacure OXE-02 manufactured by BASF as a photopolymerization initiator, and 40.7 g of propylene glycol monomethyl ether acetate as a solvent were used and mixed and stirred for 2 hours to prepare a resin composition.

(2) Examples 2 to 28 Preparation of resin composition

A resin composition was prepared in the same manner as in Example 1 except that a dye polymer compound was used instead of Synthesis Example 1 to prepare a resin composition as shown in [Table 3].

division compound division compound Example 2 Synthesis Example 2 Example 3 Synthesis Example 3 Example 4 Synthesis Example 4 Example 5 Synthesis Example 5 Example 6 Synthesis Example 6 Example 7 Synthesis Example 7 Example 8 Synthesis Example 8 Example 9 Synthesis Example 9 Example 10 Synthesis Example 10 Example 11 Synthesis Example 11 Example 12 Synthesis Example 12 Example 13 Synthesis Example 13 Example 14 Synthesis Example 14 Example 14 Synthesis Example 14 Example 15 Synthesis Example 15 Example 16 Synthesis Example 16 Example 17 Synthesis Example 17 Example 18 Synthesis Example 18 Example 19 Synthesis Example 19 Example 20 Synthesis Example 20 Example 21 Synthesis Example 21 Example 22 Synthesis Example 22 Example 23 Synthesis Example 24 Example 25 Synthesis Example 25 Example 26 Synthesis Example 26 Example 27 Synthesis Example 27 Example 28 Synthesis Example 28

(3) Comparative Example 1 Production of resin composition

A resin composition was prepared with the same composition as in Example 1 except that Victoria Blue B, a triarylmethane dye compound generally used for fiber dyeing and writing utensils, was used to prepare a resin composition.

(4) Comparative Example 2 Production of resin composition

A resin composition was prepared in the same manner as in Example 1 except that a dye compound was used instead of Synthesis Example 1 using a dye [compound b-1].

3. Evaluation Example

(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 in a convection oven at 230 ° C for 30 minutes, color characteristics were confirmed using a spectrophotometer, MCPD 3700 from Otsuka electronic Co., After the heat treatment was carried out, the color characteristic was confirmed again and the value of? Eab * was determined and shown in Table 4 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 a 1.34 W // nm (420 nm) After irradiating with the illuminance for 8 hours, the color characteristic was confirmed again, and the value of [Delta] Eab * was obtained and shown in Table 4 below.

(3) Chemical resistance measurement

After the spin coating, exposure and post-baking were carried out in the same manner as in the measurement of heat resistance, color characteristics were confirmed using a spectrophotometer, MCPD3700 manufactured by Otsuka electronic Co., Ltd., and immersed in propylene glycol monomethyl ether acetate (PGMEA) . Changes in the color characteristics of the specimens before and after immersion in the solvent were confirmed. The results are shown in Table 4 below.

division Heat resistance
ΔEab * Light resistance
ΔEab * Chemical resistance
ΔEab * division Heat resistance
ΔEab * Light resistance
ΔEab * Chemical resistance
ΔEab * Example 1 2.44 2.80 1.19 Example 2 2.48 2.33 0.44 Example 3 2.87 2.92 0.83 Example 4 2.61 2.74 0.19 Example 5 3.07 2.50 1.30 Example 6 3.12 5.33 1.22 Example 7 2.77 4.12 0.41 Example 8 2.31 3.51 0.33 Example 9 2.01 2.69 1.04 Example 10 2.87 2.48 0.46 Example 11 1.94 2.06 2.11 Example 12 2.78 4.22 0.21 Example 13 2.64 3.08 0.77 Example 14 2.09 2.97 0.13 Example 15 2.98 2.55 1.59 Example 16 2.15 2.47 2.02 Example 17 2.92 2.21 0.55 Example 18 2.99 3.04 2.31 Example 19 2.46 3.11 0.61 Example 20 3.16 3.71 2.55 Example 21 1.96 4.07 0.49 Example 22 2.12 4.62 1.89 Example 23 1.53 4.15 0.14 Example 24 2.31 5.00 0.34 Example 25 1.97 4.63 2.28 Example 26 2.33 5.46 0.48 Example 27 2.21 3.09 0.70 Example 28 2.39 2.91 2.00 Comparative Example 1 60.52 20.53 50.14 Comparative Example 2 2.65 3.01 73.04

As can be seen from the above Table 4, Examples 1 to 28 according to the present invention show excellent heat resistance, light resistance and chemical resistance. On the other hand, Comparative Example 1 using Victoria Blue B, which is a triarylmethane dye generally used in the textile industry and writing instrument, shows a remarkable decrease in heat resistance, light resistance and chemical resistance, and is used for the synthesis of the polymer compound , The heat resistance and the light resistance were good, but the chemical resistance was greatly lowered.

Claims (14)

A dye polymer comprising a structure represented by the following formula (1):
[Chemical Formula 1]

In the above formula (1)
X ^- is a bis (trifluoromethane) sulfonimide anion, nonafluorobutanesulfonic acid anion or tetrakis (pentafluorophenyl) borate anion,
R ₅ , R ₆ and Y are each independently selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms and a halogen group,
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, an allyl group, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms and a substituted or unsubstituted Benzyl group, and at least two or more of R ₁ , R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms or a substituted or unsubstituted benzyl group,
R ₇ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, n is 0 or 1, and R ₈ is hydrogen or methyl. A dye polymer compound having a structure represented by the following formula (2)
(2)

In the above formula (2)
X ^- is a bis (trifluoromethane) sulfonimide anion, nonafluorobutanesulfonic acid anion or tetrakis (pentafluorophenyl) borate anion,
R ₁₃ , R ₁₄ and Y are each independently selected from a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms and a halogen group,
R ₉ and R ₁₀ are each independently a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms or a substituted or unsubstituted benzyl group,
R ₁₁ and R ₁₂ each independently represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R ₁₅ and R ₁₆ are each independently hydrogen or methyl. 3. The method according to claim 1 or 2,
Wherein the dye polymer compound further comprises a structure represented by the following Chemical Formula 3 to Chemical Formula 6:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In the above Chemical Formulas 3 to 6,
R ₁₇ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and a substituent having 1 to 18 carbon atoms having an epoxy or oxetane substituent,
R < ₁₈ > is hydrogen or methyl,
R ₁₉ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms. The method according to claim 1,
Wherein the dye represented by Formula 1 is synthesized from a monomer represented by Formula 7:
(7)

In the above formula (7)
X ^- , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Y are the same as defined in the formula 1, R ₂₀ is represented by the following formula 1,
[Structural formula 1]

In the above structural formula 1, n, R ₇ and R ₈ are the same as defined in the above formula (1). 3. The method of claim 2,
[Formula 2] is a dye polymer compound synthesized from a monomer represented by the following Formula 8:
[Chemical Formula 8]

In the above-mentioned [Chemical Formula _{^{8], X -, R 9}} , R 10, R 11, R 12 R 13, R 14, R 15, R 16 and Y is as defined in [Formula 2]. The method of claim 3,
(3) to (6) are synthesized from monomers represented by the following formulas (9) to (12), respectively:
[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

In the above Chemical Formulas 9 to 12,
R ₁₇ , R ₁₈ And R ₁₉ are the same as defined in the formulas (3) to (6), respectively. 3. The method according to claim 1 or 2,
Wherein the dye polymer compound has a weight average molecular weight (Mw) of 2,000 to 150,000. 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 colorant is the dye polymer compound according to claim 1 or 2. 9. The method of claim 8,
Wherein the colorant further comprises at least one dye selected from xanthene dyes, cyanine dyes and azapphyrin dyes. 9. The method of claim 8,
Wherein the resin composition further comprises a blue pigment or a violet pigment. 9. The method of claim 8,
Wherein the colorant is 0.01% by weight to 50% by weight based on the total weight of the resin composition. 9. The method of claim 8,
The reactive unsaturated compound may be a thermosetting monomer or oligomer; Photocurable monomers or oligomers; And a combination thereof. The resin composition for a color filter according to any one of claims 1 to 3, 9. The method of claim 8,
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 polymer compound according to claim 1 or 2 as a colorant.