KR101515384B1 - Ink composition and manufacturing method of color filter using the same - Google Patents

Abstract

To provide an ink composition. The ink composition according to an embodiment of the present invention includes a plurality of pigment particles, and at least one block copolymer bonded to each of the plurality of pigment particles. Here, the block copolymer is represented by the following formula (1)

≪ Formula (1) >

In the above formula (1), the monomer -A- has a property of repelling the pigment particle, the monomer -B- has a property of adsorbing to the pigment particle,

The monomer (monomer) -B- adjacent to each other between the block copolymers bonded to the one pigment particle is cross-linked with each other, and the monomer-A- adjacent to each other cross-links the thermosetting reaction.

Block copolymer, thermosetting, photocuring

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition and a color filter using the same,

The present invention relates to an ink composition and a method of manufacturing a color filter using the same.

Recently, research in the display industry for application of inkjet printing has been actively conducted. As a representative example, in order to print an LCD color filter by an ink-jet method, it is required to improve accuracy, reliability, durability, and the like in fields such as inkjet ink, head, system, and measurement method.

In the case of double ink, stable dispersion stability of a durable pigment is one of the key challenges. In terms of ink ejection, the dispersing system should be adjusted to have a viscosity of from 5 to 25 cP and a surface tension of from 20 to 30 mN / m (DPMA: dipropylene glycol monomethyl ether acetate). On the printing side, The degradation of the color purity by the coloring agent should be minimized.

In the preparation of pigment dispersions, the dispersant may encapsulate the pigment by physical adsorption or by chemical adsorption. However, in the case of the method using the chemical adsorption, a stable bond is formed rather than a disadvantageous adsorption. However, in this case, it is difficult to remove by-products and excess reactants generated after the chemical reaction by dialysis and centrifugation.

The pigment dispersion for preparing a color filter ink is prepared, and further the binder and monomer components necessary for film formation are further compounded to complete the ink composition. Further organic components such as binders and monomers may lower the transmittance of the color filter layer, Can be reduced.

An object of the present invention is to provide an ink composition excellent in dispersion stability, a color filter manufactured using the same, and a method of manufacturing the same.

An ink composition according to an embodiment of the present invention includes a plurality of pigment particles and at least one block copolymer bonded to each of the plurality of pigment particles, Lt; / RTI >

      ≪ Formula (1) >

In the above formula (1), the monomer -A- has a property of repelling the pigment particles, the monomer -B- has a property of adsorbing to the pigment particles, and the block copolymers The monomer (monomer) -B- adjacent to each other is cross-linked with each other, and the monomer-A- adjacent to each other crosses the thermosetting reaction.

The monomer-A- contained in each of the neighboring pigment particles can be bonded to each other by a thermosetting reaction.

The monomer-B- adjacent to each other can be cured by UV irradiation and cross-linked with each other.

The monomer-B- adjacent to each other can cross-link each other by a crosslinking agent.

The crosslinking agent is represented by the following formula (2)

           ≪ Formula (2) >

In the above formula (2), X may be an amine group, an acid group or an epoxy group, and p may be an integer of 2 to 5.

The monomer-A- can be any one of poly (vinylbenzyl chloride), poly (vinylbenzyl azide), poly (vinylbenzophenon), and poly (vinylbenzyl cinnamate).

The monomer-B- can be any one of poly (acrylic acid), poly (methacrylic acid), poly (vinyl alcohol) and poly (vinyl phenol).

The content ratio of Am and Bn may be 3: 1 to 10: 1.

The content ratio of the pigment particles to the block copolymer may be from 1: 3 to 1:10.

Another embodiment of the present invention includes a color filter manufactured using the ink composition according to the embodiment of the present invention.

A method of manufacturing a color filter according to another embodiment of the present invention includes the steps of encapsulating the pigment particles with the block copolymer by mixing pigment particles, a block copolymer represented by the following formula (1) and a solvent,

      ≪ Formula (3) >

Cross-linking monomer-B- adjacent to each other between a plurality of block copolymers bonding with said one pigment particle, ink-jet printing an ink composition comprising a plurality of said encapsulated pigment particles, Applying heat to the composition to cross-link the adjacent monomer-A- to each other.

The step of cross-linking the monomer-B- may be cured by adding a cross-linking agent to the mixed solution or irradiating with UV.

The step of cross-linking the monomer-A- with each other is a step in which the monomer-A- adjacent to each other between the block copolymers bonded to the one pigment particle are bonded to each other, Monomer-A- can be bonded to each other.

Thus, according to the present invention, the monomer of the block copolymer oriented outward of the pigment particle thermally cures to form a color filter without the need for additional binder and monomer for film formation. Therefore, dispersion stability can be enhanced.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Also, when a layer is referred to as being "on" another layer or substrate, it may be formed directly on another layer or substrate, or a third layer may be interposed therebetween. Like numbers refer to like elements throughout the specification.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a block copolymer for explaining an ink composition according to an embodiment of the present invention. Fig.

1, a block copolymer (BC) is bonded to a pigment particle 100, and a first polymer 200 adsorbed on the pigment particle 100 is cross-linked with a micelle core ) C1 and the second polymer 300 oriented outward of the pigment particle 100 thermally cures to form a micell corona C2.

The first polymer 200 may be a photo-curable material and the second polymer 300 may be a thermoset material. In particular, the first polymer 200 may be any one of poly (acrylic acid), poly (methacrylic acid), poly (vinyl alcohol), and poly (vinyl phenol). The second polymer 300 may be any one of poly (vinylbenzyl chloride), poly (vinylbenzyl azide), poly (vinylbenzophenon), and poly (vinylbenzyl cinnamate).

The first polymer 200 can cross-link with each other by using a crosslinking agent or by irradiating UV, and the second polymer 300 can cross-link each other by applying heat. When heat is applied to the second polymer 300 for crosslinking, not only the bonding occurs between the second polymer 300 oriented outwardly of one pigment particle 100, but also the bonding between the plurality of pigment particles 100 The bonding occurs also between the second polymers 300 neighboring each other.

The ink composition according to an embodiment of the present invention can encapsulate the pigment particles 100 with a block copolymer (BC) to prevent agglomeration between the pigment dispersed particles. The block copolymer (BC) can bind to the pigment particles 100 by physical adsorption.

The block copolymer (BC) can be represented by the following chemical formula (1).

      ≪ Formula (1) >

In the above formula (1), Bn corresponds to the first polymer (200), and Am corresponds to the second polymer (300).

M is an integer of 3 to 30 and n is an integer of 1 to 10 in the above formula (1). The content ratio of Am and Bn may be 3: 1 to 10: 1.

When the content of Bn is less than the above-mentioned content, there is a disadvantage in that sufficient adsorption with the particles can not be formed, or sufficient crosslinking can not be formed, so that the dispersion stability of the pigment dispersion system may deteriorate. If the content is exceeded, the dispersibility in the solvent may be deteriorated as the Am content is insufficient.

In addition, the thickness and solvation power of the micelle can be controlled by controlling the content ratio of Am and Bn.

PVBC-b-PAA can be exemplified as a material that can be typically used as a block copolymer (BC) in an embodiment of the present invention. Poly (vinylbenzyl chloride) (PVBC) is used as a thermally curable block, and poly (acrylic acid) (PAA) can be used as a chemical crosslinkable block. PVBC-b-PAA can be prepared by the process of the following reaction formula (2).

                      ≪ Reaction formula (2) >

2 is a view illustrating a process of manufacturing a color filter using an ink composition according to an embodiment of the present invention.

Referring to FIG. 2, the pigment particles 100 can be encapsulated with a block copolymer (BC) by first mixing pigment particles 100, a block copolymer (BC), and a solvent.

When the pigment particle 100 and the block copolymer BC are mixed, the first polymer 200 adsorbs along the periphery of the pigment particle 100 in the block copolymer BC. The second polymer (300) is oriented in the outward direction of the pigment particle (100).

When the dispersing agent is encapsulated in the pigment according to the physical adsorption method, it is stabilized through continuous dynamic equilibrium between the dispersing agent and the pigment surface. Such a dynamic equilibrium state is sensitively changed depending on the concentration of the pigment particles 100, When the pigment particles 100 undergo a dilution process or the like, the agglomeration of the pigment particles 100 can be advantageously promoted.

However, in the embodiment of the present invention, the block copolymer (BC) is physically adsorbed using the physical adsorption method to form an additional crosslink in the micelle core (C1) of the encapsulated pigment to form a topological barrier A more stable ink composition can be formed.

The solvent includes alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol or isobutyl alcohol; Ketones such as acetone, methyl ethyl ketone or diacetone alcohol; Propylene glycol monomethyl ether acetate (EDGAC), propylene glycol methyl ether acetate (PGMEA), 3-methoxybutyl acetate (MBA), diethylene glycol monomethyl ether acetate Esters such as monobutyl ether acetate (DGMA); Butylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, , Polyhydric alcohols such as 1,2-hexanediol, 1,2,6-hexanetriol, hexylene glycol, glycerol, glycerol ethoxylate or trimethylolpropaneethoxylate; Lower alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; Nitrogen-containing compounds such as 2-pyrrolidone or N-methyl-2-pyrrolidone; Dimethyl sulfoxide, tetramethylene sulfone, or thioglycol, and the like, or a mixture of two or more thereof.

The block copolymer BC surrounds the pigment particles 100 to form micell C1 and the first polymer 200 adjacent to each other in one micelle C1 is crosslinked by a cross- To form the micelle (C1). Or the first polymer 200 adjacent to each other in one micelle C1 may be cured by UV irradiation and cross-linked with each other.

The crosslinking agent may be represented by the following formula (3).

            ≪ Formula (3) >

In the above formula (3), X may be an amine group, an acid group or an epoxy group, and p may be an integer of 2 to 5.

For example, the cross-linking agent may be 2,2 '- (ethylenedioxy) bis (ethylamine).

In the ink composition according to the embodiment of the present invention, known pigments may be used, and pigments coated with a dispersant, or mixtures thereof, may be used.

Specific examples of the pigment include carbon black, graphite, vitreous carbon, activated charcoal, activated carbon, anthraquinone, phthalocyanine blue, phthalocyanine green, diazos, monoazos, pyranthrones, Perylene, quinacridone and indigoid pigments. Examples of pigments coated with a dispersant include carbojet series and Orient Chemical. CW-series, etc., but the present invention is not limited thereto.

The pigment particles 100 are encapsulated by a block copolymer (BC), then ink-jet printed, and heat treated to thermally cure the micelle corona (C2) portion, thereby improving the coatability and physical properties.

FIG. 3 is a diagram showing the evaluation of the thermosetting reaction using the ink composition according to the embodiment of the present invention.

3, a material obtained by mixing 0.5w% or 0.25w% of PVBC-b-PAA with 1w% of pigment was coated on three glass substrates, one glass substrate was kept at room temperature, The two glass substrates were heated to 160 ° C, immersed in chloroform, and sonicated. After about 20 minutes, it was confirmed that the glass substrate which had not been heated had almost completely peeled off the pigment, and the remaining heated glass substrate was mostly not peeled and fixed.

4 is a graph showing dispersion stability of pigment particles according to an embodiment of the present invention.

Referring to FIG. 4, graphs are obtained by DLS (Dynamic Light Scattering) analysis to numerically confirm the dispersion stability of pigment particles. It can be seen that the dispersion stability increases remarkably when PVBC-b-PAA is used as a block copolymer, and when thermosetting is performed after printing and when the crosslinking reaction is caused by thermosetting.

The ink composition for producing a printable color filter according to an embodiment of the present invention has a surface tension of 15 to 40 dyne / cm at 25 DEG C and a viscosity of 5 to 25 cps. If the surface tension of the ink composition at 25 캜 is less than the above range, there may be a problem in the process of forming droplets during ink jetting. If the surface tension exceeds the above range, Can not do it. If the viscosity of the ink composition is less than 5 cps, there may be a problem that the ink is too thin to jet the ink droplets. If the viscosity is more than 25 cps, the fluidity of the ink deteriorates and excessive voltage is required in ink jetting. Can not do it.

The ink composition for forming a color filter according to an embodiment of the present invention may also be usefully used in the fields of textiles and displays in which inkjet printing technology is used. In particular, inkjet printing technology in the field of LCD can be applied, and it can also be used for display printing such as OTFT, OLED and the like.

In another embodiment of the present invention, there is provided a color filter manufactured using the ink composition for producing a printable color filter according to an embodiment of the present invention. Since the color filter is manufactured using an ink composition having improved dispersibility of the pigment, accuracy, reliability, durability, and the like are improved during its manufacture, thereby realizing excellent quality.

The ink composition for a printable color filter according to the present invention can be used to produce a color filter using an inkjet printing method. The ink jet printing method described above may be a commonly known method. For example, a color filter can be manufactured by forming a pixel with a black matrix on a substrate, applying an ink composition to the pixel, drying and hard baking the pixel, and forming an overcoat layer thereon.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a block copolymer for explaining an ink composition according to an embodiment of the present invention. Fig.

2 is a view illustrating a process of manufacturing a color filter using an ink composition according to an embodiment of the present invention.

3 is a diagram for evaluating a thermosetting reaction using an ink composition according to an embodiment of the present invention.

4 is a graph showing dispersion stability of pigment particles according to an embodiment of the present invention.

Description of the Related Art

100 Pigment particles 200 First polymer

300 Third polymer C1 Mycelial core

C2 Micelle corona BC block copolymer

Claims (13)

A plurality of pigment particles, And at least one block copolymer bonded to each of the plurality of pigment particles, The block copolymer is represented by the following formula (1)       ≪ Formula (1) >

In the above formula (1), the monomer -A- has a property of repelling the pigment particle, the monomer -B- has a property of adsorbing to the pigment particle, Wherein the monomer (A) -B- adjacent to each other between the block copolymers bonded to the one pigment particle are cross-linked with each other, and the monomer-A- adjacent to each other crosses the thermosetting reaction. The method of claim 1, Wherein the monomer-A- contained in each of the neighboring pigment particles is bonded to each other by a thermosetting reaction. 3. The method of claim 2, The monomer-B- adjacent to each other is cured by UV irradiation and cross-linked with each other. 3. The method of claim 2, Wherein the monomer-B- adjacent to each other is crosslinked with each other by a crosslinking agent. 5. The method of claim 4, The crosslinking agent is represented by the following formula (2)            ≪ Formula (2) >

In the above formula (2) X is an amine group, an acid group or an epoxy group, and p is an integer of 2 to 5. [ The method of claim 1, Wherein the monomer-A- is any one of poly (vinylbenzyl chloride), poly (vinylbenzyl azide), poly (vinylbenzophenon), and poly (vinylbenzyl cinnamate). The method of claim 1, Wherein the monomer-B- is any one of poly (acrylic acid), poly (methacrylic acid), poly (vinyl alcohol) and poly (vinyl phenol). The method of claim 1, Wherein the content ratio of Am to Bn is 3: 1 to 10: 1. The method of claim 1, Wherein the content ratio of the pigment particles to the block copolymer is 1: 3 to 1:10. A color filter produced using the ink composition of any one of claims 1 to 9. Mixing pigment particles, a block copolymer represented by the following formula (3) and a solvent to encapsulate the pigment particles with the block copolymer,       ≪ Formula (3) >

Cross-linking monomer-B- adjacent to each other between a plurality of block copolymers bonding with said one pigment particle, Ink-jet printing an ink composition comprising a plurality of the encapsulated pigment particles, Applying heat to the ink composition to cross-link the adjacent monomer-A- with each other. 12. The method of claim 11, Wherein cross-linking the monomer-B- is performed by adding a cross-linking agent to the mixed solution or curing the mixture by irradiation of UV. The method of claim 12, The step of cross-linking the monomer-A- Wherein said monomer-A- adjacent to each other between said block copolymers bonding to said one pigment particle is bonded, Wherein the monomer-A- contained in each of the neighboring pigment particles is bonded to each other.

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