KR20180050146A - Coloring agent and colored photosensitive resin composition comprising the same - Google Patents

Abstract

The present invention relates to a coloring agent and a colored photosensitive resin composition having the same. According to an embodiment of the present invention, the colored photosensitive resin composition comprises a dye compound and a dye high molecule. According to the present invention, the coloring agent and the colored photosensitive resin composition having the same can manufacture a color filter having high resolution.

Description

[0001] The present invention relates to a coloring agent and a colored photosensitive resin composition containing the same,

The present invention relates to a coloring agent and a colored photosensitive resin composition containing the same. More particularly, the present invention relates to a coloring agent exhibiting excellent solvent resistance and usable for producing a color filter, and a colored photosensitive resin composition containing the same.

A color filter used in a liquid crystal display device, an OLED, or the like is used for realizing a color image in a display device. The color filter can be manufactured by coating, curing and patterning a pigment on a basic substrate using various methods have.

The color filter is formed by a red, green, and blue pixel portions on a transparent substrate such as a glass. Color filters used in an image display apparatus and a solid-state image pickup device are typically red (R), green And a blue (B) coloring pattern, and serves to color the passing light or to divide the light into three primary colors. The red, green, and blue dyes are composed of fine particles, that is, a pigment. The red, green, and blue dyes are mixed with pigments having similar colors rather than being used alone to obtain color display characteristics of a desired region. Green, and blue.

BACKGROUND ART [0002] In recent years, a technology for developing a large-screen and high-definition liquid crystal display has been developed. In such a situation, a color filter used for a liquid crystal display or the like is required to have a high color purity. In order to improve the color purity, it is necessary to increase the content of the coloring matter with respect to the solid content of the photosensitive resin composition for a color filter and to make the particle size of the coloring matter more minute. In recent years, a color filter for a solid-state imaging device such as a CCD has been demanded to have higher fineness.

On the other hand, dyes and pigments used as coloring matters are required to have favorable absorption characteristics in terms of color reproducibility, good resistance to oxidizing gases such as light resistance, heat resistance and ozone under the conditions to be used, and the like.

Under such circumstances, a technique of using a dye as a pigment instead of a pigment has been proposed. In the case of using a dye instead of a pigment, it is expected to achieve high resolution by solving the problem of color unevenness and roughness in a color filter for a solid-state imaging device, and in a liquid crystal display device or an organic EL display, Is expected to improve.

However, the colorant composition containing a dye generally has a problem of insufficient light resistance, heat resistance and solvent resistance as compared with a pigment which forms a molecular aggregate.

 Further, in order to improve the color purity, it is necessary to add a large amount of dye. In this case, since the amount of other components such as a polymerizable compound or a photopolymerization initiator should be relatively reduced in the colorant composition, the curability of the composition, , And developability may be deteriorated.

Korean Patent Laid-Open Publication No. 2014-0071146 discloses a blue resin composition for a color filter comprising a triarylmethane dye polymer compound obtained by polymerizing monomers such as triarylmethane dye and acrylic acid. However, the dye polymer still has insufficient solvent resistance, and there is a problem that elution and dye transfer still occur.

Accordingly, there is a demand for development of a colorant for color filter production which overcomes the above problems and has improved solvent resistance.

Disclosure of the Invention The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a colorant having improved solvent resistance without deteriorating transparency, color characteristics, and storage stability, and a colored photosensitive resin composition containing the same.

In order to solve the above problems, according to one embodiment of the present invention,

A dye compound having a polymerizable unsaturated functional group, and a dye polymer in which a reactive monomer having a crosslinkable functional group is polymerized,

There is provided a colorant comprising crosslinked dye particles crosslinked with each other by a crosslinking agent.

Further, according to another embodiment of the present invention,

The colorant; Polymer resin; Polymerizable compounds; A photopolymerization initiator; And a coloring photosensitive resin composition comprising a solvent.

According to the colorant for a color filter of the present invention, a dye polymer in which a dye compound and a reactive monomer are polymerized is cross-linked with each other by a cross-linking agent to form a three-dimensional structure, so that it can have excellent solvent resistance to a solvent used in the production of a color filter .

In addition, the colorant for a color filter of the present invention can improve the solvent resistance without lowering the transmittance, color purity, and storage stability when compared with a dye compound which is used as such without forming a polymer or a crosslinked structure.

Therefore, when a color filter is manufactured using the colored photosensitive resin composition containing the coloring agent for a color filter according to the present invention, the phenomenon that the coloring agent is eluted by the solvent in the subsequent step or transferred to other structures is reduced, can do.

1 is a graph showing light transmittance of a colorant according to one embodiment of the present invention and a comparative example.
2 is a graph showing the solvent resistance of the colorant according to one embodiment of the present invention and a comparative example.
3 is a cross-sectional view showing the structure of a photoresist pattern and an overcoat layer formed using the colored photosensitive resin composition of the present invention.
4 is a graph showing the migration characteristics of the colorant according to one embodiment of the present invention and a comparative example.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the coloring agent of the present invention and the colored photosensitive resin composition containing the coloring agent will be described in more detail.

The colorant according to one embodiment of the present invention includes crosslinked dye particles in which a dye compound having a polymerizable unsaturated functional group and a dye polymer in which a reactive monomer having a crosslinkable functional group is polymerized are crosslinked with each other by a crosslinking agent.

The dye compound contained in the crosslinked dye particles of the present invention is known to be usable as a colorant for producing a color filter, and any dye having a polymerizable unsaturated functional group can be used without particular limitation.

The polymerizable unsaturated functional group may be an ethylenically unsaturated functional group such as an acrylate group, a vinyl group, or an acryloyl group.

Specific examples of the dye having a polymerizable unsaturated functional group as described above include dyes such as anthraquinone dyes, anilinoazo dyes, triphenylmethane dyes, pyrazole dyes, pyridone azo dyes, atrapyridone dyes, oxo A phenol dyestuff, a benzylidene dyestuff or a xanthene dyestuff. However, the present invention is not limited thereto. The resin composition for a color filter according to the present invention may contain any dye having an unsaturated functional group polymerizable with a dye compound used as a colorant. Can be used.

When the dye compound is a compound containing no polymerizable unsaturated functional group, an unsaturated functional group may be introduced into the dye compound. The method of introducing the polymerizable unsaturated functional group into the dye compound is not particularly limited and may be introduced by a general method known to a person skilled in the art. For example, an unsaturated functional group can be introduced into the dye compound by performing a nucleophilic substitution reaction with a compound having a dye compound monomer as a nucleophile and a leaving group and an ethylenically unsaturated functional group together.

In the colorant for a color filter of the present invention, a dye polymer having the polymerizable unsaturated functional group and a reactive monomer having a crosslinkable functional group are polymerized to form a dye polymer first. In the reactive monomer having a crosslinkable functional group, "reactive" means having a polymerizable unsaturated functional group and being capable of polymerization with the dye compound.

In the reactive monomer having a polymerizable unsaturated functional group and a crosslinkable functional group, the polymerizable unsaturated functional group may be an ethylenically unsaturated functional group such as an acrylate group, a vinyl group, or an acryloyl group. The crosslinkable functional group may be, for example, a hydroxyl group, a carboxyl group, an epoxy group, an amide group, an amine group, an oxetanyl group, or an isocyanate group, but the present invention is not limited thereto.

According to one embodiment of the present invention, examples of the reactive monomer having a hydroxyl group with the crosslinkable functional group include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) (Meth) acrylate, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyleneglycol (meth) acrylate, and the like.

According to an embodiment of the present invention, examples of the reactive monomer having a carboxyl group as the crosslinkable functional group include acrylic acid, (meth) acrylic acid, itaconic acid, maleic acid, and fumaric acid.

According to one embodiment of the present invention, examples of the reactive monomer having an epoxy group as the crosslinkable functional group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, or 2-glycidoxyethyl Methacrylate, and the like.

Also, according to one embodiment of the present invention, examples of the reactive monomer having an amide as the crosslinkable functional group include acrylamide, octadecyl acrylamide, isopropyl acrylamide, aminopropyl methacrylamide, or [(dimethylamino) propyl] Methacrylamide, and the like.

According to one embodiment of the present invention, examples of the reactive monomer having an amine group as the crosslinkable functional group include allylamine, 2-aminoethyl methacrylate, and en- (3-aminopropyl) methacrylamide. have.

According to one embodiment of the present invention, examples of the reactive monomer having an oxetanyl group as the crosslinkable functional group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (Acryloyloxymethyl) 3-hexyloxetane or 3- (methacryloyloxymethyl) 3-hexyloxetane, 3- And the like.

According to one embodiment of the present invention, examples of the reactive monomer having an isocyanate group as the crosslinkable functional group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4- Isocyanate butyl acrylate, and the like.

The reactive monomer having a crosslinkable functional group may be used alone, or a mixture of two or more thereof may be used.

The reactive monomer having a crosslinkable functional group may be polymerized in an amount of about 0.5 to about 30 parts by weight, or about 0.5 to about 10 parts by weight based on 100 parts by weight of the dye polymer. When the content is less than 0.5 part by weight, the crosslinking structure of the dye polymer may not be formed properly, and when the content is more than 30 parts by weight, the content of the dye compound may be relatively small and the color purity may decrease.

In addition to the reactive monomer having a crosslinkable functional group, a reactive monomer having no crosslinkable functional group may be further used for controlling the molecular weight.

The method of polymerizing the dye compound having a polymerizable unsaturated functional group and the reactive monomer having a crosslinkable functional group is not particularly limited, and a polymer can be formed by photopolymerization or thermal polymerization according to a known method.

The dye polymer formed as described above may be a linear polymer having a structure in which the reactive monomer and the dye compound are linearly connected.

The dye polymer may have a weight average molecular weight (Mw) of about 1,000 to about 100,000 g / mol, preferably about 3,000 to about 50,000 g / mol, and more preferably about 5,000 to about 30,000 g / mol. If the weight average molecular weight is too low, the solvent resistance may be lowered. If the weight average molecular weight is too high, compatibility with the solvent and the binder may be decreased. From this point of view, the degree of polymerization can be controlled to have a weight average molecular weight within the above range.

As described above, the dye polymer having a polymerizable unsaturated functional group and the dye polymer polymerized with a reactive monomer having a crosslinkable functional group are reacted with a crosslinking agent to form a structure in which the dye polymer is crosslinked with a crosslinking agent, Particles can be provided.

The crosslinking agent reacts with the crosslinkable functional group of the reactive monomer in the above-mentioned dye polymer to crosslink the dye polymer in the form of a linear polymer. Since the crosslinked structure is formed as described above, the crosslinked dye particles form a two-dimensional or three-dimensional matrix structure, and the dye compound is chemically bonded to the inside of the matrix structure of the crosslinked dye particles, It can be formulated.

The crosslinking agent is preferably contained in an amount of about 0.01 to about 10 equivalents, preferably about 0.1 to about 1 equivalent, based on 1 equivalent of the reactive monomer contained in the dye polymer. When the amount of the crosslinking agent is too small, the crosslinking reaction conversion rate is low and the effect of enhancing the solvent resistance may be deteriorated. If the crosslinking agent is included too much, the color purity may be lowered.

On the other hand, the crosslinking agent can be used without limitation as long as it is a compound capable of forming a crosslinking structure by reacting with the crosslinkable functional group of the above-mentioned reactive monomer.

For example, the crosslinking agent may be at least one selected from the group consisting of a bifunctional or higher alcohol compound, a carboxylic acid compound, an amine compound, an epoxy compound, and an isocyanate compound.

Examples of the bifunctional or higher functional alcohol compound include mono-, di-, tri-, tetra- or polyethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4- - pentanediol, polypropylene glycol, glycerol, polyglycerol, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-cyclohexanedimethanol, and the like.

Examples of the carboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, server acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tricarboxylic acid, Or ethalenediamine tetraacetic acid.

Examples of the amine compound include ethylene diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propanediamine, pentaethylenehexamine, hexamethylenediamine, decanediamine, phenylenediamine, aminopropyltrimethoxy Silane, aminopropyltriethoxysilane, polyethyleneamine, polyamidepolyamine and the like.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl Diallyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, Pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris Dicyclohexyl isocyanurate, or tris (glycidoxyethyl) isocyanurate.

Examples of the isocyanate group compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoform diisocyanate, tetramethyl xylene diisocyanate, and naphthalene diisocyanate.

The crosslinked dye particles can be used as a coloring agent in a colored photosensitive resin composition or the like used in the production of a color filter.

According to one embodiment of the present invention, the crosslinked dye particles of the present invention may have a minimum particle size of about 0.1 nm, or about 1 nm, or about 2 nm, and a maximum particle size of about 100 nm, or about 80 nm, or about 50 nm . By having a particle size range as described above, light scattering due to dye particles can be reduced, and high transmittance and contrast ratio can be realized.

According to another embodiment of the present invention, there is provided a colorant comprising crosslinked dye particles, wherein the dye polymer having the polymerizable unsaturated functional group and the dye polymer polymerized with a reactive monomer having a crosslinkable functional group are crosslinked with each other by a crosslinking agent; Polymer resin; Polymerizable compounds; A photopolymerization initiator; And a coloring photosensitive resin composition comprising a solvent.

The crosslinked dye particles contained in the colored photosensitive resin composition of the present invention are used as a colorant and have been described above.

The colorant may be at least about 10 parts by weight, or at least about 20 parts by weight, at least about 90 parts by weight, or at least about 80 parts by weight, based on 100 parts by weight of the solid contents contained in the colored photosensitive resin composition. About 50 parts by weight or less. If the content of the colorant is too low, the color purity may be lowered. If the content is too high, the curing reaction of the resin composition may not be performed properly.

As the polymer resin, those generally used in the technical field of the present invention such as an alkali-soluble polymer resin may be used. Specifically, an acrylic polymer resin containing a carboxyl group as alkali solubility can be used, and a resin having a weight average molecular weight (Mw) of 3,000 to 150,000 g / mol can be used.

The content of the polymer resin may be about 1 to about 30 parts by weight, or about 10 to about 30 parts by weight based on 100 parts by weight of the solid content of the colored photosensitive resin composition, but the present invention is not limited thereto.

The polymerizable compound may be an acrylate-based compound. Specifically, examples of the polymerizable compound include one kind selected from pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) The above compounds may be used, but the present invention is not limited thereto.

The content of the polymerizable compound may be about 1 to about 50 parts by weight, or about 10 to about 50 parts by weight based on 100 parts by weight of the solid content of the colored photosensitive resin composition, but the present invention is not limited thereto .

According to one embodiment of the present invention, the photopolymerization initiator may be 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'- (2-hydroxyethoxy) -phenyl (2-hydroxyethoxy) phenyl) -1H-pyrazolo [3,4-d] pyrimidin- 2-hydroxypropyl ketone, benzophenone, 2,4,6-trimethylaminobenzophenone, and the like, but the present invention is not limited thereto.

The content of the photopolymerization initiator may be about 0.1 to about 10 parts by weight based on 100 parts by weight of the solid content of the colored photosensitive resin composition, but the present invention is not limited thereto.

According to one embodiment of the present invention, the solvent includes methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene Propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, At least one compound selected from propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate or dipropylene glycol monomethyl ether, But is not limited thereto.

The content of the solvent is not particularly limited as it is adjustable in consideration of coating properties and workability. For example, the content of the solvent may be about 50 to about 500 parts by weight based on 100 parts by weight of the solid content of the colored photosensitive resin composition.

According to an embodiment of the present invention, the colored photosensitive resin composition may further contain a curing accelerator, a thermal polymerization inhibitor, a dispersant, an antioxidant, an ultraviolet absorber, a leveling agent, a photosensitizer, a plasticizer, Or an additive that can be included in the colored photosensitive resin composition for a conventional color filter such as a surfactant.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate) Trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris And trimethylol ethane tris (3-mercaptopropionate). However, the present invention is not limited thereto, and may include those generally known in the art.

Meanwhile, the colored photosensitive resin composition according to one embodiment of the present invention can be used for producing a color filter by a method generally known in the technical field of the present invention, for example, a printing method or a photolithography method.

For example, according to the photolithography method, the colored photosensitive resin composition is applied onto a transparent substrate by a method such as spray coating, spin coating, slit coating, roll coating, or dipping. An exposure process is selectively performed on the coating film through a mask having a predetermined pattern. Meanwhile, the pre-exposure baking and / or post-baking may be further performed. After the exposure, the colored photosensitive resin composition is developed to form a desired photoresist pattern. The developed substrate is washed and dried to obtain a color filter in which a desired type of photoresist pattern is formed.

According to the coloring agent for a color filter and the colored photosensitive resin composition containing the coloring agent of the present invention described above, the dye polymer is cross-linked with a crosslinking agent to form a three-dimensional structure in the form of particles, thereby having excellent solvent resistance.

In addition, the colorant for a color filter of the present invention can improve the solvent resistance without lowering the transmittance, color purity, and storage stability when compared with a dye compound which is used as such without forming a polymer or a crosslinked structure.

Therefore, when the colored photosensitive resin composition of the present invention is used, a color filter of high reliability and high resolution can be produced.

Best Mode for Carrying Out the Invention Hereinafter, the operation and effects of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

<Examples>

Example 1

1-1> Polymerization of Dye Polymer

9 g of triarylmethane dye monomer compound (B702, Gyeongin Co., Ltd.), 1 g of methacrylic acid (MMA: methacylic acid) and 0.9 g of azo-based polymerization initiator ABIN (azobisisobutyronitrile) were dissolved in propylene glycol methyl ether acetate) to prepare a polymerization solution.

The polymerization solution was injected into 10 g of PGMEA at 85 캜 under a nitrogen atmosphere for 2 hours by using a syringe pump. Thereafter, the reaction mixture was further stirred at 85 DEG C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated under reduced pressure, and vacuum dried to obtain a dye polymer having a Mw of 6,169 g / mol and a dispersion degree of 1.35.

1-2> Preparation of crosslinked dye particles

5 g of the dye polymer obtained in the above 1-1 was dissolved in PGMEA in a concentration of 10 wt%, and then heated to 155 ° C under a nitrogen atmosphere. Separately, 3 g of polypropylene glycol (Mw: 3,500 g / mol) was dissolved in PGMEA at a concentration of 25 wt%, and the mixture was poured into a reaction flask equipped with the dye polymer and stirred for 15 hours.

After the reaction was completed, the reaction solution was diluted with acetone and dried to obtain crosslinked dye particles.

The obtained crosslinked dye particles were observed with a scanning electron microscope (SEM) to confirm the particle shape with a particle diameter of about 5 to 50 nm.

1-3> Preparation of colored photosensitive resin composition

(Mw: 15,000 g / mol) polymerized in a weight ratio of 60:40 of benzyl methacrylate (BzMA) and methacrylic acid (MAA) of 3.5 g as crosslinking dye particles obtained in 1-2 above as a colorant, , 6 g of dipentaerythritol hexaacrylate as a polymerizable compound, 1 g of Irgacure OXE 01 (BASF) as a photopolymerization initiator, and 50 g of a solvent PGMEA were mixed to prepare a colored photosensitive resin composition.

Example 2

2-1> Polymerization of Dye Polymer

9 g of triarylmethane dye monomer compound (B702, Gyeongin Corporation), 1 g of glycidyl methacrylate and 0.9 g of azo-based polymerization initiator ABIN (azobisisobutyronitrile) were dissolved in propylene glycol methyl (PGMEA) ether acetate) to prepare a polymerization solution.

The polymerization solution was injected into 10 g of PGMEA at 85 캜 under a nitrogen atmosphere for 2 hours by using a syringe pump. Thereafter, the reaction mixture was further stirred at 85 DEG C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated under reduced pressure, and vacuum dried to obtain a dye polymer having an Mw of 22,360 g / mol and a dispersion degree of 2.11.

2-2> Preparation of crosslinked dye particles

5 g of the dye polymer obtained in the above 2-1 was dissolved in PGMEA at a concentration of 10 wt%, and then heated to 155 DEG C under a nitrogen atmosphere. Separately, 0.2 g of ethylene glycol and 0.2 g of glutaric acid were dissolved in PGMEA in a concentration of 25 wt%, and the mixture was poured into a reaction flask equipped with the dye polymer and stirred for 15 hours.

After the reaction was completed, the reaction solution was diluted with acetone and dried to obtain crosslinked dye particles.

The obtained crosslinked dye particles were observed with a scanning electron microscope (SEM) to confirm the particle shape with a particle diameter of about 5 to 50 nm.

2-3> Preparation of colored photosensitive resin composition

3.5 g of crosslinked dye particles obtained in Example 2-2, benzyl methacrylate (BzMA) and methacrylic acid (MAA) in an amount of 60:40 in terms of a weight ratio of acrylic binder resin (Mw: 15,000 g / mol ), 6 g of dipentaerythritol hexaacrylate as a polymerizable compound, 1 g of Irgacure OXE 01 (BASF) as a photopolymerization initiator, and 50 g of a solvent PGMEA were mixed to prepare a colored photosensitive resin composition.

Comparative Example 1

A colored photosensitive resin composition was prepared in the same manner as in Example 1-3, except that 3.5 g of the dye polymer obtained in Example 1-1 was used in place of the crosslinked dye particles obtained in Example 1-2 above as a colorant.

Comparative Example 2

Except that 3.5 g of a triarylmethane-based dye monomer compound (B702, manufactured by Kyorin Co., Ltd.) was used instead of the crosslinked dye particles obtained in Example 1-2 above as a colorant, to obtain a colored photosensitive resin composition .

Comparative Example 3

A colored photosensitive resin composition was prepared in the same manner as in Example 2-3, except that 3.5 g of the dye polymer obtained in Example 2-1 was used in place of the crosslinked dye particles obtained in Example 2-2 as a colorant.

<Experimental Example>

Evaluation of light transmittance and solvent resistance

The light transmittance of the colored photosensitive resin compositions of Examples 1 and 2 and Comparative Examples 1, 2 and 3 was evaluated by the following method. The resin compositions of Examples 1 and 2 and Comparative Examples 1, 2 and 3 were used to evaluate the solvent resistance after forming a photoresist pattern as follows.

(1) Light transmittance

The light transmittance according to wavelength was measured using a UV / VIS spectrophotometer.

A graph of measurement results of Examples 1 and 2 and Comparative Examples 1, 2 and 3 is shown in FIG.

(2) Solvent resistance

Each of the photosensitive resin compositions of Examples and Comparative Examples was coated on a transparent glass substrate (5 cm x 5 cm) using a spin coater to a thickness of 2 m. Then, it was pre-baked at a temperature of 100 DEG C for 100 seconds, and then exposed using an exposure apparatus at an exposure dose of 40 mJ / cm &lt; ^{2 &} gt ;. The exposed substrate was developed using an alkaline developer and post baked at 230 캜 for 20 minutes to prepare a test sample having a photoresist pattern formed thereon.

The specimens were immersed in NMP (N-methyl-2-pyrrolidone) solution at a temperature of 80 ° C for 40 minutes, and the absorbance of the eluate was measured according to the wavelength.

A graph of absorbance measurement results of Examples 1 and 2 and Comparative Examples 1, 2 and 3 is shown in FIG. 2, and the measured values are shown in Table 1 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Absorbance 0.495 0.583 0.758 1.939 0.632

1, the resin composition of the embodiment comprising the crosslinked dye particles of the present invention as a coloring agent shows a large difference in light transmittance according to wavelengths as compared with the resin composition of the comparative example comprising the dye compound or the dye polymer as a coloring agent It can be seen that optical characteristics are maintained even by polymerization and crosslinking.

Also, referring to FIG. 2 and Table 1, when the absorbance of the eluate eluted after immersion in NMP was compared with that of the comparative example, the absorbance of the eluted solution was greatly reduced, showing improved solvent resistance.

Dye Dissolution and Dye Evaluation by Post-Process

(4) Elution and migration evaluation by post-processing (formation of an overcoat layer)

A photoresist pattern and an overcoat layer were formed by the structure shown in Fig.

More specifically, each of the resin compositions of Examples 1 and 2 and Comparative Examples 1, 2 and 3 was coated on a transparent glass substrate 10 having a thickness of 5 cm x 5 cm and a thickness of 0.1 T to a thickness of 20 m using a spin coater . Then, it was pre-baked at a temperature of 100 DEG C for 100 seconds, and then exposed using an exposure apparatus at an exposure dose of 40 mJ / cm &lt; ^{2 &} gt ;. The exposed substrate was developed using an alkaline developer and post baked at 230 캜 for 20 minutes to prepare a test piece having the photoresist pattern 20 formed thereon.

Then, the overcoat resin composition was applied onto the photoresist pattern 20 of the specimen to form the overcoat layer 30. [

The light transmittance was measured at the intermediate point P1 of the transparent glass substrate 10 located between the photoresist patterns after the formation of the overcoat layer for the evaluation of the dye transfer, and the measurement result graph is shown in FIG.

In order to evaluate dye elution, the chromaticity coordinates of the intermediate point P2 of the photoresist pattern before and after the formation of the overcoat layer were measured, and the color difference? Eab thereof was shown in Table 2 below.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 △ Eab 2.43 3.12 8.51 15.52 11.68

Referring to FIG. 4 and Table 2, the photoresist pattern formed using the crosslinked dye particles of the present invention showed color difference due to dye elution before and after the overcoat layer process was much smaller than that of the comparative example, The light transmittance was almost 100% over the wavelength range of 420 to 700 nm, and the dyeing problem of the eluted dye hardly appeared.

Therefore, when the color filter is manufactured using the crosslinked dye particles of the present invention, the solvent resistance is expected to be remarkably improved.

Claims (10)

A dye compound having a polymerizable unsaturated functional group, and a dye polymer in which a reactive monomer having a crosslinkable functional group is polymerized,
A colorant comprising crosslinked dye particles crosslinked with each other by a crosslinking agent.
The method according to claim 1,
Wherein the dye polymer has a weight average molecular weight (Mw) of 1,000 to 100,000 g / mol.
The method according to claim 1,
Wherein the polymerizable unsaturated functional group is an ethylenically unsaturated functional group.
The method according to claim 1,
The reactive monomer is a polymerizable unsaturated functional group and contains an ethylenically unsaturated functional group. The crosslinkable functional group includes at least one kind selected from the group consisting of hydroxyl group, carboxyl group, epoxy group, amide group, amine group, oxetanyl group and isocyanate group &Lt; / RTI &gt;
The method according to claim 1,
Wherein the crosslinking agent comprises at least one selected from the group consisting of an alcohol compound having two or more functional groups, a carboxylic acid compound, an amine compound, an epoxy compound, and an isocyanate compound.
The method according to claim 1,
Wherein the reactive monomer having a crosslinkable functional group is contained in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the dye polymer.
The method according to claim 1,
Wherein the crosslinking agent is contained in an amount of 0.01 to 10 equivalents based on 1 equivalent of the reactive monomer contained in the dye polymer.
The method according to claim 1,
Wherein the crosslinked dye particles have a particle diameter of 0.1 nm to 100 nm.
A colorant according to claim 1; Polymer resin; Polymerizable compounds; A photopolymerization initiator; And a solvent.
10. The method of claim 9,
10 to 90 parts by weight of the colorant, 1 to 30 parts by weight of the polymer resin, 1 to 50 parts by weight of the polymerizable compound, 100 parts by weight of the polymeric resin, And 0.1 to 10 parts by weight of a photopolymerization initiator.

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